b i o m a s s a n d b i o e n e r g y 3 7 ( 2 0 1 2 ) 2 2 9 e2 3 6

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Hemicellulose extraction from aspen chips prior to kraft

pulping utilizing kraft white liquor

Ai Jun a, Ulrike W. Tschirner b,*, Zachary Tauer a

a
Department of Bioproducts and Biosystems Engineering, University of Minnesota, 203 Kaufert Lab, 2004 Folwell Avenue,
St.Paul, MN 55108, USA
b
Department of Bioproducts and Biosystems Engineering, University of Minnesota, 204 Kaufert Lab, 2004 Folwell Avenue,
St.Paul, MN 55108, USA

article info abstract

Article history: Pre-extraction of hemicelluloses before commercial pulping processes such as kraft
Received 4 February 2011 pulping has been considered as one potential approach to generate fermentable sugars as
Received in revised form feedstock for biofuels and bioproducts. In this study kraft white liquor with 18% active
11 October 2011 alkali and 25% sulfidity was used to partially extract xylan from commercial aspen chips.
Accepted 9 December 2011 Reaction temperatures of 70e90
C and reaction times of 1e4 h were explored. Amount of
Available online 29 December 2011 xylan extracted increased with increasing time and temperature. The extracted xylan was
recovered using ultrafiltration. We were able to recover xylan at levels of up to 48 g kg1 of
Keywords: dry original chips. Pre-extracted chips were used for subsequent kraft pulping. The ultra-
Hemicellulose filtration permeate was utilized as cooking liquor without any additional processing and
Pre-extraction without additional chemical addition. Due to the pre-extraction the lignin removal in
Ultrafiltration subsequent kraft processes was significantly faster; offering the option of reducing cooking
Permeate time and increasing mill throughput. Pulp yield remained in the same range as the control.
Kraft pulping Physical properties of pulps made from pre-extracted aspen chips showed similar strength
properties as the control runs if compared at given lignin content. Pre-extraction of aspen
chips using existing kraft white liquor appears to be a viable approach in an attempt to
produce a side stream of fermentable sugars in an existing pulp mill.
ª 2011 Elsevier Ltd. All rights reserved.

1. Introduction minimize the environmental impacts, black liquors are

Pulp and Paper industry is characterized by commodity-
pricing and intense competition and currently faces the
challenge of having to compete in a global market against low
cost producers and rising local wood prices. Over 90% of all
chemical pulps in the U.S. are currently produced using the
kraft pulping process. During kraft pulping, hemicelluloses
are removed and partially degraded into low molecular weight
isosaccharinic acids and accumulate in the black liquor
together with degraded lignin. To recover energy and the
inorganic chemicals used in the pulping process and to
concentrated and burned. As the heating value of hemi-
celluloses is considerably lower than that of lignin, extracting
the hemicelluloses before the pulping stage for generation of
high value products has the potential to increase the revenue
streams and improve overall economics [1,2].
Removal of hemicelluloses from wood as a pre-treatment
step has been practiced commercially for some years in the
production of “dissolving pulps”. In this process, the hemi-
celluloses are removed to allow the production of pure cellu-
lose. The yield of these processes is lower than in kraft pulping
(mass fraction of around 40% vs. 50% in pulping) and the

* Corresponding author. Tel.: þ1 612 624 8798; fax: þ1 612 625 6286.
E-mail addresses: aixxx012@umn.edu (A. Jun), ulrike@umn.edu (U.W. Tschirner), tauer025@umn.edu (Z. Tauer).
0961-9534/$ e see front matter ª 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2011.12.008
230 b i o m a s s a n d b i o e n e r g y 3 7 ( 2 0 1 2 ) 2 2 9 e2 3 6
cellulose thus obtained after the “dissolving” process has
significantly lower degree of polymerization (DP) than the
original raw material. Since dissolving pulps are processed
into products such as cellulose nitrate, cellulose xanthate
(rayon fibers) and cellulose acetate, the shorter cellulose
chains are an advantage. In pulping, on the other hand,
shorter cellulose chains translate into lower pulp yield,
strength loss, and lower quality fiber. The most common
commercial processes for extracting hemicellulose from dis-
solving pulps are pre-steaming to release natural wood acids
(autohydrolysis) followed by water extraction or acid hydro-
lysis with small amounts of mineral acids.
Pre-extraction of hemicellulose before subsequent
commercial pulping has been considered for some time now [3].
Several research groups are exploring various pre-treatments of
lignocellulosic materials including the use of water or steam.
These processes are called autohydrolysis, hydrothermolysis or
hydrothermal pre-treatment [4e9]. Autohydrolysis generally
requires a treatment temperature of 180e200
C. Due to the
formation of natural wood acids (pH 3.5e4.5), autohydrolysis
results in removal of hemicellulose in the form of oligosugars.
Unfortunately, at high temperatures the sugar yield is reduced
due to side reactions generating byproducts such as furfurals. In
addition, the low pH initiates significant random chain cleavage
of the cellulose chain, resulting in lower degree of polymeriza-
tion and the formation of new reducing end groups. Wood chips
pre-extracted with acid or hot water at low pH show signifi-
cantly increased peeling reactions in the subsequent high
alkaline kraft process, resulting in unacceptably high yield loss
[9]. Yoon and Van Heiningen [8] observed an additional mass
fraction loss based on the weight of dry original wood mass of
3e6% in subsequent pulping for southern pine chips pretreated
with autohydrolysis. Autohydrolysis of aspen chips in our
laboratory showed an additional mass fraction loss of up to 12%
[9]. Acid or autohydrolysis pre-treatment before kraft pulping
suffers from serious drawbacks and hence is not likely to be
suitable for commercial biofuel production from hemicellulose
in concert with an existing bio-based operation such as a pulp
mill. Acid and autohydrolysis, instead, due to the degrading
effects on cellulose, appears to be better suited for processes
where the remaining biomass (cellulose and hemicellulose) is
converted to fermentable sugars, not papermaking fiber.
Other methods for hemicellulose extraction include mild
alkaline solutions with and without addition of cations such
as Na, K, Li and borate at low temperatures [10e12]. As re-
ported by Yoon et al. [13], mild alkali extraction of mixed
hardwood with green liquor or 30 g kg1 NaOH (based on dry
mass of wood) or with Na2CO3 at 140
C and 90 min reaction
time removed a mass fraction of about 6e8% of the starting
wood material and resulted in a final pH close to neutral. In
a subsequent kraft pulping step the pulp yield was lowered by
a mass fraction of approximately 1% as compared to the
control. A modified pre-extraction through addition of
0.5 g kg1 AQ with 30 g kg1 Na2CO3 or 30 g kg1 green liquor
(all based on dry wood mass), however, increased the yield to
a mass fraction 1% higher than conventional kraft pulp. This
process showed no significant difference in paper strength in
handsheet tests except for a minor change in tear resistance.
Unfortunately, the hemicellulose yield for this mild alkali
process appears to be very low. The majority of the
60e80 g kg1 of wood material removed in this case is ex-
pected to be the acetyl groups since hardwoods contain
approximately 40 g kg1 of acetyl groups based on dry wood
mass which are rapidly released under alkaline conditions
[14,15]. This mild alkali pre-treatment process uses high
temperatures and hence requires costly pressurized vessels
and significantly increases capital costs. In addition, the final
pH of the mild alkali process is around 7.0 and the extracted
xylans are recovered in the form of low molecular weight
oligosugars, which are more difficult to concentrate than
higher molecular polymers.
To overcome some of the drawback of the low alkali pre-
extraction we have developed a novel pre-extraction process
for hardwoods, using highly alkaline systems, completely
compatible and synergistic with commercial kraft processes
[16]. We used NaOH at levels of 160 g kg1 to 330 g kg1 based
on dry wood mass at atmospheric pressure and low tempera-
tures (below 100
C). In addition to higher xylan yield (40 g kg1
to 50 g kg1 dry wood) while maintaining fiber yield and
quality and thereby the overall paper properties, our approach
also has the potential for lower operating and capital costs
since the pre-extraction is done at atmospheric pressures and
low temperatures [16].
Subsequent kraft pulping of the extracted wood chips
demonstrated that the pulp yield could be maintained or even
increased by (10e20) g kg1 dry wood as compared to the
control (not pre-extracted wood chips), alleviating one of the
key concerns for pulp and paper manufacturers. In addition to
maintaining quality and yield, we also demonstrated
decreased residence times in the kraft process thus resulting
in potentially increased pulping capacity or the option of using
lower cooking temperatures [16]. Although hemicellulose
extraction can have negative impact on pulp properties
[17,18], optimizing the extraction and pulping conditions
allowed full control over the cellulose/hemicellulose ratio and
hence fiber and pulp properties [16]. In order to make the high
alkaline pre-extraction approach commercially viable and
economically feasible, all the chemicals from the extraction
stage have to be recovered and reused. We concluded that
a logical step forward for a high alkaline pre-extraction
process would be to replace the NaOH used in our earlier
studies with white liquor, already present in the pulp mill. The
results of pre-extraction with white liquor before subsequent
kraft pulping are presented in this study.
2. Materials and methods
2.1. Materials
All experiments were conducted using commercial aspen
wood chips (Populus tremuloides) donated by Sappi Fine Paper
(Cloquet, MN). The chips were screened and fractions >12 mm
and <25 mm were collected, air dried, sorted to remove knots
and bark, and then stored in plastic drums. Moisture content
of chips was determined immediately before use, using TAPPI
test methods T210-cm-03 [19]. Chemicals used for pre-
extraction and pulping (NaOH, Na2S  9H2O) were purchased
from SigmaeAldrich and used as is.
 b i o m a s s a n d b i o e n e r g y 3 7 ( 2 0 1 2 ) 2 2 9 e2 3 6
2.2. Pre-extraction
40 g of air dry chips were mixed with 160 mL of white liquor
(Active Alkali 18% and Sulfidity 25%) and filled into a rotating
stainless autoclave submerged in an oil bath. The autoclave was
allowed to rotate at room temperature for 1 h to allow complete
wetting of the chips with white liquor, then the oil bath
temperature was raised at a rate of 2.33
C min1 to the desired
reaction temperature. Pre-extraction conditions selected were:
70
C for 2 h and 4 h; 90
C for 1 h, 2 h, 3 h and 4 h. After pre-
extraction, the liquor was separated from the chips and chips
were used as is for subsequent pulping procedures (no washing
or drying). All experiments were performed in triplicate.
2.3. Hemicellulose separation from extraction liquor
The liquor from the pre-treatment process was filtered using
a Millipore Stirred Ultrafiltration Cell, Model 8200, a poly-
ethersulfone membrane (MWCO 10,000 Da) and pressure of
310e345 kPa. The retentate (concentrated material remaining
in the filtration unit) was analyzed for glucan, xylan and lignin
content. The permeate (liquid filtered through the membrane)
was mixed with the pretreated chips for the next pulping
process. The final yield of xylan was calculated based on the
mass of the original oven dry chips.
2.4. Subsequent pulping with permeate
The permeate was applied as cooking liquor with no further
cleaning or addition of chemicals. The pulping was carried out in
rotating stainless autoclaves with the amount of pretreated chips
equal to 40 g dry mass (see 2.2), and a total of 160 mL of the
permeate using varying H-factors (see Table 4). The permeate
addition was adjusted to account for remaining liquor in chips.
2.5. Biomass analysis
2.5.1. Lignin and carbohydrates
Klason lignin content of wood chips and pulp was measured
in accordance with the method described in NREL method
NREL/TP-510-42618 [20]. The samples were air dried, ground
and hydrolyzed in a water bath for 1 h at 30
C with concen-
trated H2SO4 (mass fraction 72%). Then the solution was
diluted with deionized water and heated in an autoclave at
120
C for another hour. The hydrolyzed solution was allowed
to cool to room temperature and the acid-insoluble lignin was
filtered off and weighted after drying at 105
C (Klason lignin).
Acid soluble lignin was determined from the hydrolyzed
solution (after removal of Klason Lignin) using a Varian
UV/VIS Spectrophotometer according to NREL method NREL/
TP-510-42618 [20]. The samples were diluted as necessary to
bring the absorbance into the range of 0.3e0.7. Samples were
scanned at 240 nm. A sulfuric acid solution was used as blank.
Acid soluble lignin was calculated using the absorptivity
constants provided in the NREL methods [20].
In addition, for pulp samples Kappa numbers were deter-
mined using TAPPI test method T236 cm-85 [21]. Kappa
number should only be used for pulps with a yield of less than
mass fraction of 70% and is defined as the volume in mL of
standardized aqueous solution of potassium permanganate
231
consumed by 1 g of moisture-free pulp under acidic conditions
at 25
C for 10 min.
Pulp was screened on a Huygen slotted vibratory screen
separator (Model 1600, Huygen Corp.) using a 0.15 mm slotted
screen and yield (mass fraction of pulp based on original non-
extracted chip mass) and rejects (mass fraction of material not
passing screen) were determined.
Carbohydrates were determined using the HPLC method
described in the Laboratory Analytical procedure NREL
method NREL/TP-510-42618 [20]. The analysis was conducted
using a Waters HPLC with a VARIAN MetaCarb 87P analytical
column with a Bio Rad De-ashing cartridge in line. The oper-
ating conditions were 3720 kPa with a 0.3 mL min1 flow rate
at 80
C of the column temperature. Acetyl group content was
determined by hydrolyzing aspen material ground to pass
a 0.4 mm opening screen with H2SO4 solution having an
amount-of-substance concentration of 2 mol L1 at 95
C for
3 h and determining acetic acid content using an HPLC and
acetic acid standards. Analysis was run in triplicate.
2.5.2. Molecular weight of xylan
Xylan molecular weight was determined through size exclu-
sion chromatography (SEC) using a Waters HPLC system with
Waters 1525 Binary Pump, a Waters 717 plus Autosampler,
a Waters 2414 Refractive Index Detector and Breeze software
for operation control and data processing. The separations
were performed using two Waters ultrahydrogel columns
connected in series (300 mm  7.8 mm; pore size 250 Å and
120 Å) and packed with hydroxylated polymethacrylate based
gel. Water flowing at 0.5 mL min1 was used as eluent. The
columns temperature was kept at 30
C. Polyethylene glycol
standard (PEG, Polymer Laboratories) and xylose (Acros) were
used for calibration.
2.5.3. Total sulfur analysis
Total elemental analyzer for solids, S-144 DR from LECO
Corporation was used for total sulfur analysis. A sample was
dried at 65
C until crisp, passed through a stainless steel
grinder with 0.84 mm sieve and mixed thoroughly. A
0.100e0.150 g sample was weighed into a ceramic boat and
covered with about 0.5 g of tungsten oxide (ComCat-LECO
Corp.). The sample was combusted in a furnace at a temper-
ature of 1371
C in an oxygen rich atmosphere. This produces
SO2 which is carried by the oxygen stream to an LECOS S-144
DR infrared detector where it is quantified.
2.5.4. Properties of handsheets
Standard handsheets were made using TAPPI test method
T205-88 [22]. Pulp slurries with a consistency of 3 g L1 were
prepared and formed into standard sheets with mass between
1.14 g and 1.25 g. Physical properties (tensile, tear, burst) were
measured using TAPPI standard test method T220-88 [22] after
conditioning the handsheets in a controlled humidity room.
3. Results and discussion
We are proposing a process for pre-extraction of commercial
aspen chips using kraft white liquor. This process could be
integrated into an existing pulp mill with minimal investment
232 b i o m a s s a n d b i o e n e r g y 3 7 ( 2 0 1 2 ) 2 2 9 e2 3 6

Biofuel feed stock

Hemicelluloses Ultra filtration Permeate
chemicals
or Retentate unit

Liquor

Extractor Preextracted Digester

Wood chips chips Pulp Paper

Proposed
Process
White
Liquor

Energy Recovery Black

Boiler Liquor

Fig. 1 e Process of pulping with hemicelluloses extraction unit using white liquor.

and process changes. Fig. 1 describes the proposed process
flow. Aspen chips will be pre-extracted with white liquor
under atmospheric conditions, the liquor will be drained from
the chips and the chips are moved to the digester without any
further treatment (no washing). The extraction liquor will
undergo an ultrafiltration process to remove the majority of
the extracted hemicelluloses. The permeate is added as
cooking liquor to the chips in the digester. No additional
chemical addition is proposed.
3.1. Hemicellulose extraction
The overall goal of this research is the pre-extraction of xylan
from commercial aspen chips using existing white liquor before
subsequent kraft pulping. After pre-extraction at varying
temperatures and times all chip residues were analyzed to
determine overall composition of the pre-extracted chips as
compared to the starting material (Table 1). Mass fraction
recovered after the pre-extraction was 84.7e90.4% based on
oven dried mass of chips going into the extraction process. Chip
yield clearly was decreased with increasing reaction time and
increasing reaction temperature. The composition analysis and
chip yield allowed us to calculate actual loss of the different
wood components during the extraction (Table 2). The extrac-
tion pre-treatment did not show a significant effect on cellulose
loss, but as expected strongly influenced the hemicelluloses
content (Table 1 and Table 2). At lower temperatures and shorter
reaction times the observed cellulose mass fraction loss was
0.2e0.4%, only at the most severe treatment of 90
C and 4 h did it
increase to 0.9%. The standard error for glucan mass fraction
loss in our experiments was determined to be 0.4e0.8% (out of
three runs). As expected for aspen chips galactose, mannose and
arabinose have very low starting concentrations (mass fraction
below 2%) and do not significantly contribute to material loss
during extraction pre-treatment. There is a reduction in Klason
lignin mass fraction of 0.8e1.2% (standard error for lignin mass
fraction loss  0.2e0.5%). The loss of Klason lignin is fairly
constant at all extraction treatments and does not appear to be
significantly influenced by reaction time or temperature. The
majority of material loss in the pretreated chips clearly comes
from xylan (34e73 g kg1 of dry chip mass) and “others”
(50e57 g kg1 of dry chip mass). Our category “others” includes
acetyl and uronic acid groups from hemicelluloses and inor-
ganics. Inorganic mass fraction of the original wood chips was
determined to be only 0.6% and is not expected to contribute
significantly to material loss. On the other hand, the acetyl group

Table 1 e Composition of aspen chips (P. tremuloides) untreated and after pre-treatments with white liquor under varying
conditions.
Mass fraction, % of Mass fraction, % (based on dry chip mass) after pre-treatment
original dry chips

70 C 4 h 90
C 1 h 90
C 2 h 90
C 3 h 90
C 4 h

Glucan 44.10  0.6 49.77  0.6 49.72  0.4 50.70  0.8 51.53  0.8 52.36  0.5
Xylan 19.60  0.3 18.37  0.4 18.20  0.4 17.63  0.4 15.57  0.4 14.91  0.5
Galactan 1.80  0.1 2.04  0.1 2.05  0.1 2.09  0.1 2.12  0.1 2.18  0.1
Arabinan 0.80  0.04 0.91  0.03 0.91  0.03 0.81  0.05 0.71  0.04 0.85  0.1
Mannan 2.00  0.2 2.27  0.2 2.28  0.4 2.32  0.4 2.48  0.5 2.30  0.4
Klason lignin 21.20  0.2 22.90  0.4 23.09  0.3 23.67  0.2 23.94  0.5 24.24  0.3
Acid soluble lignin 3.02  0.5 2.21  0.2 2.01  0.3 1.95  0.5 1.78  0.4 2.03  0.2
Othersa 5.28  0.5 1.53  0.2 1.74  0.30 1.83  0.3 1.88  0.2 1.12  0.2
Total recovered 100 90.4 90.4 88.4 87.0 84.7

a “Others” includes extractives, acetyl and uronic acids groups and inorganics. Mass fraction of inorganic material of original chips was
determined to be 0.6% based on dry chip mass. Acetyl group mass fraction of original chips was determined to be 4% based on dry chip mass.
 b i o m a s s a n d b i o e n e r g y 3 7 ( 2 0 1 2 ) 2 2 9 e2 3 6 233

do not include hemicelluloses dissolved but remaining with

Table 2 e Mass fraction removed from aspen chips during
extraction with kraft white liquor under varying the chips or material remaining in the permeate. The highly
conditions. concentrated xylan can be further cleaned using solvent
precipitation or washing processes. As mentioned before,
Mass fraction loss, % (based on dry chip mass)
after pre-treatment cellulose was resistant to the chemicals used under the
studied pre-treatment conditions and very little glucose was
70
C 4 h 90
C 1 h 90
C 2 h 90
C 3 h 90
C 4 h found in the retentate. Since we are using kraft white liquor
Glucan 0.2  0.05 0.2  0.05 0.40  0.1 0.4  0.1 0.9  0.2 for our pre-extraction step we were concerned about possible
Xylan 3.4  0.1 3.4  0.2 4.4  0.1 6.4  0.2 7.3  0.2 retention of sulfur compounds with the fermentable sugar.
Galactan 0 0 0 0 0 Elemental analysis of hemicelluloses extracted with our white
Arabinan 0 0 0.1  0.05 0.2  0.06 0.1  0.04
liquor process showed low mass fraction of sulfur of
Mannan 0 0 0 0.1  0.05 0.1  0.05
0.91e1.08% based on the air dried retentate solid. Additional
Klason 1.0  0.2 1.0  0.1 0.8  0.1 0.9  0.2 1.2  0.2
Lignin cleaning steps, such as solvent precipitation or washing
Othersa 5.0  0.3 5.0  0.3 5.9  0.5 5.2  0.4 5.7  0.5 should be able to even further reduce sulfur content. Detailed
fermentation experiments are needed to determine impact of
a “Others” includes extractives, acetyl and uronic acids groups,
remaining sulfur and other potential inhibitors on biofuels
acid soluble lignin and inorganics.
production and will be part of a subsequent study.

mass fraction in our original aspen chips was determined to be
4% (0.1%) on o.d. wood. It is well know that saponification of
acetyl groups occurs rapidly under alkaline conditions [16,17],
which explains the rapid large loss in our “others” category.
Most important of course is the observed removal of xylan.
Xylan extraction clearly depends on reaction time as well as
reaction temperatures. At the pre-treatment temperature of
90
C xylan removal increases steadily with increased
extraction time. The lower reaction temperature of 70
C
shows the same xylan content removal rate at 4 h extraction
time than the 90
C extraction at only 1 h. It should be noted
that all reaction temperatures used allowed for atmospheric
reaction conditions and did not require pressurized vessels.
The xylan extracted under these strongly alkaline condi-
tions is in polymeric form. We were able to determine that the
molecular weight of this polymer is higher than 21,000 Da. The
higher molecular weight allowed the use of ultrafiltration with
fairly large membrane pores (10,000 Da) and low pressure
(310e345 kPa). Since concentration of hemicelluloses clearly
will be a requirement to obtain a useful starting material for
biofuels fermentation processes or other applications this
improvement will have a significant positive impact on the
economics of the proposed process.
Analysis of the concentrated retentate, the material
retained by the membrane in the filtration step, showed high
xylan content (Table 3); it contained 75e96 g L1 xylan and
20e60 g L1 glucan. Considering the total amount of retentate
recovered, this equals a xylan mass fraction of 3.8e4.8% based
on the original dry aspen chips. These xylan yield calculations
only include the hemicelluloses recovered in the retentate, they
3.2. Subsequent pulping
After pre-treatment the chips were directly moved to the
digester and pulped using the permeate of the ultrafiltration
obtained from the same chip batch. Adjustments were made
to take into consideration that during the pre-treatment
process the chips absorbed white liquor which stayed with the
chips since we did not wash or dry the chips. In addition, the
overall chip solid mass changed due to material loss in the
pre-treatment stage and permeate addition rate was adjusted
to account for this material loss. The permeate had a pH of
12.89 (original white liquor pH 13.98) and was used as is, no
additional chemicals were added to the system. Clearly, the
permeate has a reduced alkalinity as compared to the original
kraft white liquor, but due to the pre-treatment overall
consumption of alkali is reduced in the subsequent pulping
process. For example the majority of acetyl groups have been
removed during pre-treatment, resulting in lower alkali
consumption during the actual pulping process. All pulping
and paper testing experiments were performed using chips
that had been exposed to extraction at 90
C and varying
reaction times (1e4 h). We selected the higher temperature
due to the potential of extracting higher levels of xylan in
shorter amount of time.
Several different H-factor conditions were chose for the
pulping (Table 4). H-factor is a pulping variable combining
time and temperature into one variable. In our studies we did
not vary pulping temperature; all cooks were performed at
170
C. This means H-factor variation simply expresses vari-
ations in cooking time. The pulp properties observed with

Table 3 e Xylan and glucan content of retentate remaining after ultrafitration concentration.
Pre-treatment Concentration in Mass fraction, Mass fraction of extracted xylan,
conditions retentate g L1 of retentate % in o.d retentate % based on original dry chip mass

Xylan Glucan Xylan Glucan

70 C 4 h 75.39 2.12 19.52  0.76 0.55  0.04 3.77  0.56


90 C 1 h 79.59 2.53 20.46  0.45 0.65  0.08 3.98  0.67


90 C 2 h 82.36 4.43 21.01  0.66 1.13  0.12 4.12  1.05


90 C 3 h 86.74 5.45 21.63  0.58 1.36  0.10 4.32  0.89


90 C 4 h 96.58 6.44 22.66  0.61 1.51  0.0.15 4.82  1.21
234 b i o m a s s a n d b i o e n e r g y 3 7 ( 2 0 1 2 ) 2 2 9 e2 3 6

Table 4 e Results of pulping experiments with pretreated wood chips.

Chip H-factora Rejects mass Yieldb Kappa Residue Klason lignin Reduction of Klason
fraction, %b mass fraction, % number mass fraction, % lignin mass fraction, %,
based on control pulp

Reference 558 1.12  0.5 51.8  3.5 25  0.1.2 3.31  0.10

90
C 1 h 558 0.94  0.2 52.5  2.4 24.3  0.8 3.25  0.08 1.81
90
C 2 h 558 0.87  0.4 51.9  3.5 23.8  0.7 3.17  0.12 4.23
90
C 4 h 558 0.74  0.8 52.1  2.5 23  0.7 2.81  0.07 15.11
Reference 671 0.75  0.5 53.3  3.0 22.5  0.9 3.28  0.05
90
C 1 h 671 0.62  0.4 52.8  4.1 21.7  0.7 3.2  0.10 2.44
90
C 2 h 671 0.31  0.3 53.1 20.9  1.2 3.07  0.11 6.40
90
C 4 h 671 0.28  0.2 53.6  2.8 19.8  0.9 2.67  0.11 18.6
Reference 711 0.66  0.5 52.5  3.2 21.9  1.1 3.08  0.10
90
C 1 h 711 0.34  0.3 53.4  3.1 20.8  1.0 2.75  0.08 10.71
90
C 2 h 711 w0.1 54.0  4.2 19.8  0.8 2.71  0.15 12.01
90
C 4 h 711 w0.1 53.2  2.1 18.6  0.7 2.40  0.15 22.08
Reference 824 0.27  0.5 52.8  2.3 19.2  1.0 2.87  0.07
90
C 1 h 824 0.1 53.1  3.2 18  1.1 2.53  0.09 11.84
90
C 2 h 824 <0.05 53.4  4.1 17.1  0.8 2.43  0.10 15.33
90
C 4 h 824 <0.05 52.8  4.2 16.2  0.8 2.27  0.06 20.91
Reference 940 <0.05 51.2  2.3 17.8  1.2

a H-factor is a variable combining time and temperature into one variable during Kraft pulping. All our Kraft cooks were performed at 170
. Here
variations in H-factor express variations in cooking time.
b Yield calculations are based on dry mass of original chips.

varying pre-treatment conditions and designated H-factors
are summarized in Table 4 and Fig. 2. The control samples
(without pre-treatment) showed the highest Kappa number
and the highest Klason lignin content for all H-factors. Lower
lignin content translates in reduced need of bleaching chem-
icals. Fig. 2 demonstrates the relationship between the
H-factor and Klason lignin content under different pre-treat-
ment conditions. As expected, for a given H-factor the lignin
content and the Kappa number decrease with increasing pre-
treatment severity (Fig. 3, Table 4). For example, at an H-factor
of 558, the Klason lignin mass fraction for the control chips
was 3.31%. It decreased to mass fraction of 3.25% with 90
C
and 1 h pre-treatment and to 3.7% and 2.81% with 2 h and 4 h
pre-treatment at 90
C respectively. It is clearly demonstrated,
that the longer the pre-treatment time, the higher the reduc-
tion of lignin content at given cooking conditions. Another
way of considering these findings is the potential for reduced
cooking time to given lignin content. For example, Klason
lignin mass fraction at 558 H-factor and 4 h 90
C pre-treat-
ment is 2.81%. To reach the same lignin mass fraction with the
Residual lignin mass fraction, %
control chips (no pre-treatment) the cook has to be extended
to an 824 H-factor. For a pulping temperature at 170
C this
means an 18 min longer cooking time for the control.
3.3. Effect of pre-treatment on physical properties of
paper
Using the pulps generated in Section 3.2 standard handsheets
were made following TAPPI test methods T205-88 [21].The
physical properties of the papers with different pre-treatments
and different H-factors are summarized in Table 5. At given H-
factor tensile index, burst and tear index all improved with the
pre-treatment. This of course is due to the reduced lignin
content. For mechanical properties of paper, lignin content is
a critical factor. The main purpose of chemical pulping is to
remove lignin, to allow easy fiber separation and easy bleach-
ing. Up to some point, the more lignin is removed, the more
bonding will take place between the cellulosic fibers to improve
25.0
Reduction of Klason lignin mass fraction, %

3.5 20.0
based on reference

3
2.5 15.0

2
10.0
1.5
1
5.0
0.5
0
0.0
558 671 711 824 558 671 711 824
H factor H-factor
Reference 90 °C-1 h 90 °C-2 h 90 °C-4 h 90°C 1 h 90°C 2 h 90°C 4 h

Fig. 2 e Effect of pre-treatment on residue lignin under Fig. 3 e Effect of pre-treatment on reduction rate of residual
different H-factors. Klason lignin.
 b i o m a s s a n d b i o e n e r g y 3 7 ( 2 0 1 2 ) 2 2 9 e2 3 6 235

Table 5 e Physical properties of paper in relation to lignin content.

Pre-extracted H-factor Tensile index Burst kPa Tear index Klason lignin mass Kappa number
wood chips kNm/kg Nm2/kg fraction, %

Reference 558 37.5  2.8 158.0  11.2 6 0.5 3.31  0.10 25  0.1.2
90
C 1 h 558 39.4  3.4 159.5  10.8 6 1.2 3.25  0.08 24.3  0.8
90
C 2 h 558 40.3  2.8 164.8  10.5 8 0.8 3.17  0.12 23.8  0.7
90
C 4 h 558 44.8  3.0 177.6  9.5 7 0.9 2.81  0.07 23  0.7
Reference 671 39.8  2.0 159.3  13.5 5 0.8 3.28  0.05 22.5  0.9
90
C 1 h 671 41.3  3.1 155.5  12.8 7 1.0 3.2  0.10 21.7  0.7
90
C 2 h 671 40.8  3.5 170.1  10.4 7 1.2 3.07  0.11 20.9  1.2
90
C 4 h 671 46.6  2.6 187.5  15.7 8 0.8 2.67  0.11 19.8  0.9
Reference 711 42.3  3.5 160.2  11.2 5 1.1 3.08  0.10 21.9  1.1
90
C 1 h 711 44.5  3.8 176.0  12.4 7 2.3 2.75  0.08 20.8  1.0
90
C 2 h 711 45.4  4.1 184.5  15.6 7 1.8 2.71  0.15 19.8  0.8
90
C 4 h 711 44.8  3.8 190.4  14.1 9 2.1 2.40  0.15 18.6  0.7
Reference 824 41.7  3.0 169.7  12.4 7 0.4 2.87  0.07 19.2  1.0
90
C 1 h 824 40.2  3.5 176.6  9.4 7 0.8 2.53  0.09 17.1  0.8
90
C 2 h 824 40.8  2.8 179.8  15.6 9 1.1 2.43  0.10 16.2  0.8
90
C 4 h 824 42.9  2.5 185.8  14.1 9 1.0 2.27  0.06 17.8  1.2

the mechanical properties of paper. However, as the pulping pre-extracted pulps is small (Table 6). Pulps from pre-
progresses and less lignin is present, cellulose becomes more extracted chips show slightly increased cellulose content
susceptible to degradation, resulting in decreased paper (maximum difference between cellulose mass fraction of
strength. It therefore is advisable to compare strength prop- control and pre-extracted 1.5%) and slightly decreased xylan
erties at given lignin content instead of given H-factor. For content (maximum mass fraction difference 1.7%). We expect
example, the control cook at H-factor 824 resulted in a Klason these differences to impact beating, but we do not expect
lignin mass fraction of 2.87% and tensile index of them to be detrimental. Walton et al. was able to show that
41.7 kNm kg1, while a 4 h pre-treatment at 90
C with an H- strength properties of mixed southern hardwoods after mild
factor of 558 and similar lignin mass fraction (2.81%) gave alkali pre-extraction actually increased after beating [23].
handsheet with a tensile strength of 44.8 kNm kg1. Burst Interestingly, the pulp yield (based on dry mass of original
strength and Tear index follow the same pattern. Obviously the chips) remains essentially unaffected throughout all of our
shorter exposure to high temperatures and the reduced alka- experiments (pulp mass fraction 51e53% with standard error
linity in the actual cooking stage helped reduce cellulose of 2% to 4%) based on original dry chip mass. All reject
degradation. Kappa number of lower than 19 and lignin mass levels were low (mass fraction below 1%), indicating that all
fraction of less than 2.4% resulted in pulps with slightly cooks reached the fiber separation point.
decreased strength properties. As mentioned before excessive
lignin removal will result in cellulose degradation and strength
loss. For our given pre-treatment times cooking should not be
extended past H-factor 711 to avoid cellulose degradation. 4. Conclusion
It is known that hemicelluloses content of pulps influences
the beating behavior and therefore the final strength proper- This preliminary study demonstrated that the use of existing
ties of paper. Conventional kraft pulping is known to degrade kraft white liquor to pre-extract aspen wood chips before
significant amounts of the xylan present in wood; xylan mass commercial kraft pulping is a viable option to obtain a stream
fraction in the control pulp at H-factor 711 was only 18.3%. of fermentable sugars. Our process showed acceptable yields
Since our pre-treatment removed low levels of hemicelluloses of polymeric hemicelluloses (mass fraction up to 4.8% based
the difference in pulp composition between control and on o.d chips) that could effectively be concentrated in an
ultrafiltration stage to concentrations of up to 97 g L1 using
high pore sizes and low pressure. Considering the need for
highest possible hemicelluloses yield pre-extraction at 90
C
Table 6 e Composition analysis of pulps from H-factor had a clear advantage as compared to the lower 70
C condi-
711 cooks; comparison of control pulp with pre-extracted tions. The permeate from the ultrafitration can effectively be
pulps. used as pulping liquor without any additional treatments and/
Concentration in % or additional chemical addition. It also was shown that paper
properties after subsequent kraft pulping actually benefited
control 90C 1 h 90C 2 h 90 C 4 h from the pre-treatment. If compared at the same lignin
Glucan 74.6  1.4 75.3  2.1 76.4  1.8 76.1  2.0 content pulps originating from runs with pre-extraction
Xylan 18.3  0.5 16.5  0.6 16.1  0.5 16.6  0.5 required shorter cooking times and resulted in paper with
Galactan 1 0.1 1  0.08 0.8  0.1 0.8  0.1 the same or slightly improved strength properties. This effect
Arabinan 0.3  0.05 0.5  0.08 0.4  0.1 0.5  0.08
is likely due to the reduced exposure to high temperature at
Mannan 0.8  0.05 0.7  0.04 0.7  0.04 0.7  0.05
high pH in the cooking stage. No change in overall pulp yield
Klason Lignin 3.08  0.10 2.75  0.08 2.81  0.15 2.4  0.15
was observed.
236 b i o m a s s a n d b i o e n e r g y 3 7 ( 2 0 1 2 ) 2 2 9 e2 3 6

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