Bioresource Technology 96 (2005) 1249–1255

Conversion of bark-rich biomass mixture into fermentable sugar

by two-stage dilute acid-catalyzed hydrolysis
a,b,*
Kyoung Heon Kim , Melvin Tucker b, Quang Nguyen b

a
Division of Food Science, College of Life and Environmental Sciences, Korea University, Seoul 136-713, Republic of Korea
b
National Renewable Energy Laboratory, Biotechnology Division for Fuels and Chemicals, Golden, CO 80401, USA

Received 5 January 2004; received in revised form 22 October 2004; accepted 22 October 2004
Available online 19 December 2004

Abstract

Despite high availability and low cost, bark has not actively been considered as a biomass feedstock for producing bio-based
products due to its high content of extractives and lignin. In this study, to investigate the feasibility of utilizing bark-rich sawmill
residues for producing value-added materials, the mixed Hemlock hog fuel/pin chips (85:15 by dry weight) from a local sawmill were
converted into fermentable sugar by two-stage dilute sulfuric acid-catalyzed hydrolysis. Combining the sugar yields from the first-
stage (190 °C for 150 s with 1.1% acid) and second-stage (210 °C for 115 s with 2.5% acid) hydrolyses, which aimed to maximize the
recovery of mannose/galactose and glucose, respectively, 13.6 g of glucose (46% theoretical maximum), 10.5 g of mannose and galac-
tose (98% theoretical maximum), and 2.8 g of xylose (85% theoretical maximum) were obtained per 100 g of the original dry
feedstock.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: Two-stage dilute acid-catalyzed hydrolysis; Bark; Sawmill residues; Hemlock; Softwood; Biomass; Pretreatment; Sugar

1. Introduction technologies using steam (Ballesteros et al., 2002), sulfu-

Lignocellulosic biomass is the most abundant renew-
able resource on earth (Bellamy, 1974), and has
attracted continuing efforts to produce fuels and chemi-
cals for a long time (Lynd et al., 1999; Sherrard and
Kressman, 1945; Sudha et al., 1998). Since lignocellu-
losic biomass is naturally recalcitrant to enzymatic
hydrolysis, pretreatment is essential to improve its
enzyme digestibility and also to obtain solubilized sugar.
Currently, dilute acid-pretreatment (i.e., hydrolysis)
using sulfuric acid (Nguyen et al., 2000) is considered
to be a near-term option, among various pretreatment
*
Corresponding author. Address: Division of Food Science,
College of Life and Environmental Sciences, Korea University, Seoul
136-713, Republic of Korea. Tel.: +82 2 3290 3028; fax: +82 2 925
1970.
E-mail address: khekim@korea.ac.kr (K.H. Kim).
ric acid (Harris et al., 1945), sulfur dioxide (Mackie
et al., 1985), carbon dioxide (Kim and Hong, 2001),
ammonia (Holtzapple et al., 1991), and NaOH/H2O2
(Curreli et al., 2002).
In previous studies on converting softwood to etha-
nol (Kim et al., 2001, 2002a,b; Nguyen et al., 1998,
2000), a two-stage dilute acid-catalyzed hydrolysis pro-
cess was developed using a steam explosion reactor to
achieve the maximum yield of soluble sugar (e.g., 80–
90% of theoretical yield from hemicellulose and 50–
60% of theoretical yield from cellulose) with cellulase
digestibility higher than 90% of the theoretical maxi-
mum. In the two-stage dilute acid-catalyzed hydrolysis,
hemicellulose, which is solubilized at less severe condi-
tions compared to cellulose, is mainly hydrolyzed in
the first stage, then the cellulose that survived in the
first stage becomes the main target in the second stage.
Because the two-stage dilute acid hydrolysis solubilizes

0960-8524/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2004.10.017
1250 K.H. Kim et al. / Bioresource Technology 96 (2005) 1249–1255
more than 50% of the cellulose overall, the total enzyme
requirement in subsequent enzymatic cellulose hydroly-
sis would be substantially reduced.
The hog fuel and pin chips are byproducts of sawmills.
The hog fuel is obtained from debarking process after
logs are soaked in hot water. The pin chips are screen
rejects from pulp chips produced from discarded veneer
and log cores. The hog fuel mainly consists of bark that
is higher in extractives and lignin and lower in cellulose
and hemicellulose compared to whole trees. Therefore,
the presence of the bark could be adverse for the hydro-
lysis of cellulose and hemicellulose. Due to rapid
increases in the price of biomass feedstock, hog fuel with
high availability and low price could be a potential feed-
stock for producing bio-based products. There have been
only a few reports on the hydrolysis of bark, such as the
SO2 pretreatment of softwoods containing bark at 9%
(Boussaid et al., 2001) and the dilute acid-pretreatment
of hardwood bark (Torget et al., 1991). However, the
complete conversion of bark-rich softwood feedstock
into fermentable sugars has not been reported yet. In
this study, to assess the feasibility of using the high-bark
sawmill waste for producing value-added bio-based prod-
ucts, the sawmill residues composed of softwood Hem-
lock hog fuel (85%, w/w) and pin chips (15%) were
tested to maximize the conversion of their cellulose and
hemicellulose fractions into fermentable hexose, such
as glucose, mannose, and galactose, through the two-
stage dilute acid-catalyzed hydrolysis process.
2. Methods
2.1. Feedstock preparation
Feedstock collection: The two types of Hemlock resi-
dues consisting of hog fuel and pin chips were collected
from a local sawmill in the US. The samples were stored
in a refrigerator before being processed.
Feedstock milling and screening: The hog fuel consists
of mainly large chunks of bark, and the pin chips con-
tain some bark and coarse, thin chips. To facilitate the
hydrolysis of the feedstock, milling and screening were
conducted. Using a knife mill (Model 10 · 12, Reduc-
tion Technology, Leeds, AL, USA), the hog fuel was
milled through a 3/4-inch screen. Over-sized particles
were screened using a 1/2-inch square-opening wire
mesh, and milled again through a 1/2-inch screen. Pin
chips were screened using the 1/2-inch square-opening
wire mesh, and the over-sized particles were screened
through a 1/2-inch screen. After the milled hog fuel
and the pin chips were thoroughly mixed, representative
samples were taken for determining the total solids con-
tent (TS) and compositional analyses as described in
Section 2.4. Both samples were stored in sealed plastic
bags and kept refrigerated.
Feedstock mixing: The milled hog fuel and pin chips
were thoroughly mixed using a blend of 85% hog fuel
and 15% pin chips based on dry weight. A representative
sample was taken for determining the TS and composi-
tional analysis of the mixed feedstock. The material was
sealed in plastic bags inside plastic drums and kept
refrigerated.
2.2. First-stage dilute acid-catalyzed hydrolysis
Acid-impregnation and partial drying: The well-mixed
feedstock was placed in a Hastelloy C-276 wire-mesh
basket and submerged for 6 h in a circulating bath of
50 °C dilute sulfuric acid in the range of 0.5–1.0 wt%,
which was determined to give the final target acid con-
centration inside biomass considering the dilution effect
by the moisture in the feedstock. The mass ratio of li-
quid (including water in the original biomass feedstock)
to dry feedstock was approximately 12:1. After over-
night draining, the acid-soaked feedstock was mixed
four times by coning and quartering. A representative
sample was taken from the mixed acid-impregnated
feedstock, and the TS of the mixed chips was determined
in triplicate using a 105 °C drying oven. The TS of the
acid-impregnated feedstock after overnight draining
was 33.7 wt% for the mixed hog fuel/pin chips.
To obtain acid-impregnated feedstock with TS higher
than 40 wt%, the acid-soaked feedstock that were
drained overnight were dewatered by air drying at 40
°C using a rotary drum dryer (a cloth dryer modified
for drying biomass materials). To avoid diminished
effectiveness of hydrolysis from pressing, as observed
in a previous study (Kim et al., 2002b), we used air dry-
ing as an alternative dewatering method for pressing.
The total drying time was 50 min for 5.0 kg of the mixed
hog fuel/pin chips. The dryer was placed on top of an
electronic platform scale (FH-133-II, Cardinal Scale
Manufacturing, Webb City, MO, USA) to monitor the
weight of the wood chips during drying. After drying,
the acid-impregnated feedstock was mixed by coning
and quartering, and a representative sample was taken.
To measure the final acid concentration of liquid en-
trained inside the partially-dried feedstock, 100 g of bio-
mass was extracted with 1000 mL of deionized water at
40 °C after overnight shaking. The extracted acid solu-
tion was filtered through a 0.2 lm membrane, then
titrated with 0.5 N standard NaOH solution (J.T. Baker,
Phillipsburg, NJ, USA). The TS of the acid-impregnated
and partially air-dried mixed hog fuel/pin chips was 46.0
wt%. The acid concentration of liquid entrained inside
the partially air-dried biomass was 1.1 wt% for the
mixed hog fuel/pin chips. In this paper, the sulfuric acid
concentration of softwood feedstock enumerated under
conditions of hydrolysis is expressed as the acid concen-
tration of entrained liquid in the partially air-dried
feedstock.
 K.H. Kim et al. / Bioresource Technology 96 (2005) 1249–1255
First-stage hydrolysis: Using a batch type 4-L steam
explosion reactor, 6 batches at 190 °C and three batches
at 185 °C were hydrolyzed at different residence times to
establish the optimum hydrolysis conditions for the first-
stage hydrolysis of the acid-impregnated and air-dried
mixed hog fuel/pin chips (1.1% acid and 46.0% TS).
The severity of the dilute acid-hydrolysis of lignocellu-
lose was represented by the combined severity parameter
as defined by Chum et al. (1990). The combined severity
(CS) combines the effects of reaction time, t (min), reac-
tion temperature, T (°C), and pH of the reaction mixture
as follows:
  
T ÿ 100
CS ¼ log10 t exp ÿ pH:
14:75
The pH of reaction mixture used in the combined sever-
ity was determined by estimating the hydronium ion
concentration from sulfuric acid after taking the dilution
effect by condensed water possibly formed from steam
due to the temperature difference between steam and
biomass (see Table 1).
2.3. Second-stage dilute acid-catalyzed hydrolysis
Washing, acid-impregnation, and partial drying: The
hydrolysate obtained from the optimum first-stage pro-
duction run giving the maximum yield of mannose/
galactose was slurried to 7 wt% TS with 50 °C water
in a 30-gal (114-L) plastic barrel. The solids were filtered
with a large (60-cm) Buchner funnel, and the cake was
washed with water. This washing step was repeated four
to five times until the pH of the filtrate measured 6.5–7.0
to essentially remove all the soluble materials. The
washed first-stage solids were re-impregnated in a 10
wt% slurry condition with dilute acid solution for 6 h
in 30-gal (114-L) plastic barrels. The acid-impregnated
first-stage materials were vacuum-filtered using the
Buchner filter, and these filtered acid-impregnated feed-
stocks were partially air-dried using the rotary dryer. As
listed in Table 2, three batches of partially dried, acid-
impregnated first-stage hog fuel/pin chips having three
different TS were prepared for the second-stage
hydrolysis.
Table 1
Compositions of Hemlock hog fuel, pin chips, and the mixture of hog fuel (85 wt%) and pin chips (15 wt%) in weight percent of dry feedstock (means
and standard deviation)a
Feedstock Glucose Mannose Galactose
Hemlock hog fuel 25.4 ± 0.3 6.3 ± 0.1 2.2 ± 0.0
Hemlock pin chips 44.0 ± 0.5 13.0 ± 0.0 3.3 ± 0.0
Mixed hog fuel/pin 29.7 ± 0.3 8.2 ± 0.7 2.4 ± 0.0
chips
a
Carbohydrate compositions are shown as hydrolyzed sugar since the analysis involves complete hydrolysis of these components using sulfuric
acid.
1251
Second-stage hydrolysis: The vacuum-filtered or par-
tially air-dried, acid-impregnated first-stage hydrolysate
solids were hydrolyzed at various conditions using the
same steam explosion reactor used in the first stage.
The hydrolysis conditions for the mixed hog fuel/pin
chips were 2.4% and 2.5% (w/w) sulfuric acid concentra-
tions, 210 °C, and 90–180 s, which correspond to CS
ranging from 2.91 to 3.26. These second-stage hydrolysis
conditions were established based on the previous
results from the two-stage hydrolysis of softwood forest
thinning (Nguyen et al., 2000).
2.4. Sample analyses
The total mass recovery yield (not including volatiles)
is the dry weight recovery expressed as a percentage of
the dry weight of input biomass (i.e., dry weight of
acid-impregnated biomass before hydrolysis), in which
the dry weight is determined after drying overnight in
a 105 °C oven. In acid-impregnated pretreated biomass,
samples were neutralized with 0.5 N NaOH solution be-
fore oven drying to prevent possible mass loss occurring
in the presence of heat and acid, which was observed in
previous preliminary experiments. All biomass samples
from solid and liquid fractions were analyzed in tripli-
cate according to National Renewable Energy Labora-
tory (NREL) Standard Biomass Analytical Procedures
(National Renewable Energy Laboratory, 2004). The
feedstock compositions (acid-soluble, Klason lignin, or-
ganic acids, ash, and individual sugar components) were
analyzed by Hauser Laboratories (Boulder, CO, USA)
according to the NREL Standard Biomass Analytical
Procedures as shown in Table 1. The sugar analysis of
the hydrolysate slurry was performed by using HPLC
(high performance liquid chromatography) with an
Aminex HPX-87P cation exchange column derivatized
with lead (Bio-Rad, Hercules, CA, USA). The total sol-
uble sugar including both monomers and oligomers was
determined after the additional hydrolysis of liquid sam-
ples at 4% (w/w) final sulfuric acid concentration and
121 °C for 1 h to convert oligomers into monomers. To
correct the sugar loss due to the degradation during the
additional hydrolysis, sugar standards were also hydro-
lyzed at the same condition. The total sugar content
Xylose Arabinose Extractives Klason Acid-soluble Acetic Ash
lignin lignin acid
2.9 ± 0.1 2.4 ± 0.1 19.8 ± 0.9 38.1 ± 0.3 0.8 ± 0.0 1.2 ± 0.0 2.4 ± 0.0
4.3 ± 0.0 1.4 ± 0.0 5.9 ± 0.1 30.2 ± 0.3 0.6 ± 0.0 2.0 ± 0.0 0.8 ± 0.0
3.3 ± 0.0 1.7 ± 0.0 15.5 ± 0.9 39.4 ± 0.4 0.6 ± 0.0 1.2 ± 0.0 1.2 ± 0.1
1252 K.H. Kim et al. / Bioresource Technology 96 (2005) 1249–1255

Table 2
Feedstock preparation for the second-stage hydrolysis
Feedstock After washing After acid-impregnation After air-drying
Total solids Acid conc. Total solids Acid conc. Total solids Acid conc.
(%, w/w) (%, w/w) (%, w/w) (%, w/w) (%, w/w) (%, w/w)
First-stage pretreated hog fuel/pin chips 27.1 0.0 29.5 2.5 N/Aa N/Aa
First-stage pretreated hog fuel/pin chips 27.1 0.0 26.1 1.3 41.1 2.4
First-stage pretreated hog fuel/pin chips 27.1 0.0 26.8 1.0 49.5 2.5
a
Not applicable.

was used in conjunction with the monomeric sugar con- 8

tent to determine the content of oligomeric sugar. The
7
detailed experimental procedures can be found in NREL
Standard Biomass Analytical Procedures (National

(g/100 g dry raw feedstock)

Total solub le sugar yield
6
Renewable Energy Laboratory, 2004). The sugar yields
from the first- and second-stage hydrolyses were calcu- 5
Mannose
lated based on the theoretical maximum yields of indi- Galactose
vidual carbohydrate components and the total dry 4 Glucose
weight of the starting biomass.
3

2
3. Results and discussion
1
1.9 2.0 2.1 2.2 2.3 2.4 2.5
3.1. First-stage dilute acid-catalyzed hydrolysis Combined severity (log R o- pH)

To establish optimum conditions (i.e., to obtain the
highest conversion yield for mannose and galactose
which are readily fermented by yeast among hemicellu-
losic sugars) for the first-stage hydrolysis of the acid-
impregnated and air-dried Hemlock hog fuel/pin chips
(1.1% acid and 46.0% TS), several hydrolysis runs were
carried out at 185 and 190 °C, as summarized in Table 3.
The sugar yields obtained from the hydrolysis runs are
plotted with respect to the combined severity factor in
Fig. 1. The highest mannose/galactose yield, 92%, was
achieved by 2.5-min hydrolysis at 190 °C, which corre-
sponds to a CS of 2.20. As hydrolysis time extended
beyond 2.5 min, lower mannose/galactose yields were
obtained possibly due to the destruction of hemicellu-
lose at the harsher conditions. However, the glucose
Fig. 1. Yields of total fermentable soluble sugar (i.e., mannose,
galactose, and glucose) from the first-stage hydrolysis of mixed
Hemlock hog fuel/pin chips at various combined severities.
yield increased as the severity of hydrolysis conditions
increased in the tested CS range as the cellulose shows
higher crystallinity than hemicellulose. The first stage
was intended to obtain the maximum mannose/galactose
yield, and the remaining cellulose could be further hydro-
lyzed into glucose in the second stage. Therefore, the
optimum first-stage conditions were selected based on
the yield of mannose and galactose such as 2.5-min reac-
tion time, 190 °C, and 1.1% acid, which gave 7.0 g of
mannose, 2.8 g of galactose with 3.2 g of glucose per
100 g of dry raw feedstock.

Table 3
First-stage hydrolysis of the mixture of Hemlock hog fuel (85 wt%) and pin chips (15 wt%)a
Run # Temp. Time Acid in biomass Combined severity Soluble sugar yield
(°C) (s) (wt%) (log Ro–pH) (% theoretical)b
Man + Gal Glu Xyl
814-1 185 120 1.1 1.96 83 10 76
814-2 185 180 1.1 2.13 85 11 78
814-3 185 240 1.1 2.26 82 11 75
813-1 190 120 1.1 2.10 80 10 72
731-1 190 150 1.1 2.20 92 10 78
732-2 190 180 1.1 2.28 84 11 76
801-1 190 210 1.1 2.34 82 14 70
801-2 190 240 1.1 2.40 70 12 67
a
Total solid content of all the input feedstock used in the experiments was 46.0 ± 0.7% (w/w).
b
Indicates total monomeric and oligomeric soluble sugars.
 K.H. Kim et al. / Bioresource Technology 96 (2005) 1249–1255 1253

100 The dip of monomeric sugar percentage in CS 2.25–

2.35 at 190 °C could to be explained by the relations
between the three reactions of polymers into oligomers
in total soluble sugars (%)

80
and oligomers into monomers and monomers into deg-
Monomeric sugar

radation products, and this requires a further kinetic

60
study with more data in the pertinent CS range. To com-
Man, 185oC
Gal, 185oC
pletely convert oligomeric sugar remaining at relatively
40 Glu, 185oC high levels in the hydrolyzed material hydrolyzed at a
high temperature for a short period into monomeric su-
Man, 190oC
20 Gal, 190oC gar, a slightly-high temperature, which is not high en-
Glu, 190oC ough to destroy monomeric sugar, hold for converting
0 after the first-stage hydrolysis may be necessary. There-
1.9 2.0 2.1 2.2 2.3 2.4 2.5 fore, the oligomeric sugar was included in the yield cal-
Combined severity (log Ro - pH)
culation of total soluble sugar in this study.
Fig. 2. Monomeric fractions in the total soluble sugar recovered in the
first-stage hydrolysis of mixed Hemlock hog fuel/pin chips at various 3.2. Second-stage dilute acid-catalyzed hydrolysis of
combined severities.
mixed hog fuel/pin chips

The percentage of monomeric sugar in total soluble
sugar produced in first-stage hydrolysis, which varied
from 72% to 100% depending on hydrolysis time and
temperature, is shown in Fig. 2. For mannose and galac-
tose, the percentage of monomeric sugar was higher at
185 °C than at 190 °C both at similar CS. This implies
that at the same CS, higher temperature and shorter res-
idence time results in higher total soluble sugar yield,
but lower monomeric sugar fraction in the soluble sug-
ars. The increase of sugar yield rather than sugar degra-
dation at a higher temperature may be attributed to the
relatively larger portion of fast-reacting hemicellulose
requiring higher activation energy for hydrolysis reac-
tion compared to the activation energy for degradation
of solubilized sugars (Esteghlalian et al., 1997). In gen-
eral, the fraction of monomeric sugar increased with
increasing CS at both temperatures except for the range
of CS 2.25–2.35 where the dips of monomeric sugar
yields were found for the case of temperature 190 °C.
For the second-stage pretreatment of the mixed hog
fuel/pin chips, the input materials of three different total
solids (TS) were prepared from the first-stage hydro-
lysate solids obtained under the conditions of 2.5 min,
190 °C, and 1.1% acid. The preparation steps included
washing, acid impregnation, and dewatering (i.e., vac-
uum filtration or partial air-drying depending upon
TS). In an actual industrial process, the solubilized sugar
in the first stage recovered before the remaining solids
proceed to second-stage hydrolysis (Kim et al., 2001,
2002a; Nguyen et al., 1998, 2000).
The total soluble sugar yields from the second-stage
hydrolysis conducted at 210 °C and 2.5% acid by vary-
ing reaction time and the TS of the acid-impregnated
materials (i.e., 30%, 41%, and 50%) are shown in Table
4. As shown in Fig. 3, the effect of TS on the recovery
yield of glucose, which is the main target in the second
stage, was noticeable. As the TS increased, the glucose
yield markedly increased. It appears that the increase

Table 4
Second-stage hydrolysis of the washed first-stage hydrolysate of Hemlock hog fuel (85 wt%) and pin chips (15 wt%)
Run # Temp. Time Acid in biomass Total solids Combined severity Total soluble sugar yield combining
(°C) (min) (wt%) (wt%) (log Ro–pH) first and second stages (% theoretical)
Man + Gal Glu Xyl
1023-1 210 100 2.5 50 2.96 96 43 88
1023-2 210 115 2.5 50 3.02 98 46 85
1023-3 210 150 2.5 50 3.14 98 44 88
1010-1 210 105 2.4 41 2.97 100 39 88
1010-2 210 90 2.4 41 2.91 94 39 82
925-1 210 120 2.4 41 3.03 97 41 76
925-2 210 150 2.4 41 3.13 95 40 85
925-3 210 180 2.4 41 3.21 95 36 82
926-1 210 120 2.5 30 3.08 94 33 85
926-2 210 150 2.5 30 3.18 94 30 82
926-3 210 180 2.5 30 3.26 94 30 82
1105-4 210 90 2.5 30 2.95 96 37 82
1105-5 210 105 2.5 30 3.20 102 37 82
1254
20
Glucose yield from two stages
(g Glu/g dry raw feed stock)
15
10
5
0 0
2.9 3.0 3.1
Combined severity in the 2nd stage
Fig. 3. Combined total soluble glucose yields of the first and second
stages after the second-stage hydrolysis of the mixed Hemlock hog
fuel/pin chips at 2.4–2.5% acid, 30%, 41%, and 50% TS, and 210 °C.
of glucose yield with increasing TS relates to the
enhanced transfer of steam and heat through less wet
materials since the hydrolysis is carried out in a rela-
tively short time. Therefore, the TS of input materials
is also an important factor in addition to temperature,
time, and acid concentration in biomass.
The maximum glucose yield combining both first-
and second-stage hydrolysis was 46% of the theoretical
maximum, which was equivalent to 13.6 g total soluble
glucose/100 g dry raw feedstock. This was achieved at
210 °C, 115 s, 2.5% acid, and 50% TS (i.e., CS = 3.02).
In other studies on the two-stage hydrolysis of softwood
feedstock, in which the feedstock were mostly bark free,
the glucose yields were 57–60% of the theoretical maxi-
mum (Nguyen et al., 2000; Soderstrom et al., 2003). The
lower glucose yield in this study may be attributed to the
high content of bark in the sawmill residues. This result
may impose challenges in developing a commercial bio-
conversion process using the bark-rich feedstock despite
its availability and low price.
Also, in Table 4 the recovery of the hexose sugar de-
rived from the hemicellulose of Hemlock, mannose and
galactose, through the two-stage hydrolysis, was close to
100% of the theoretical maximum. Therefore, unlike
glucose, the recovery of hemicellulosic sugar did not
seem to be affected by the high content of bark in the
feedstock. A similar result was reported when the SO2-
catalyzed hydrolysis of softwood containing bark (9%)
and no bark were compared (Boussaid et al., 2001).
The xylose yield from the hemicellulose was only 76–
88% of the theoretical maximum, possibly due to its deg-
radation into furfural since the hydrolysis conditions did
not aim at the maximum recovery of unfermentable xy-
lose by yeast. As shown in Fig. 4, as much as 10.0–10.9
and 2.7–2.9 g per 100 g of dry raw feedstock of
mannose/galactose and xylose were obtained from both
K.H. Kim et al. / Bioresource Technology 96 (2005) 1249–1255
12
(g total sugar/100 g raw dry feedstock)
30% TS
Total soluble sugar from two stages
41% TS 10
50% TS
TS 30%, Man+Gal
8 TS 30%, Xyl
TS 41%, Man+Gal
6 TS 41%, Xyl
TS 50%, Man+Gal
TS 50%, Xyl
4
2
2.8 2.9 3.0 3.1 3.2 3.3
3.2 3.3
Combined severity
Fig. 4. Combined total soluble mannose, galactose, and xylose yields
of the first and second stages after the second-stage hydrolysis of mixed
Hemlock hog fuel/pin chips at 2.4–2.5% acid, 30%, 41%, and 50% TS,
and 210 °C.
the first and second stages. Because the hemicellulosic
sugar was mainly hydrolyzed in the first stage, the yield
differences in the second stage were not significantly
reflected.
4. Conclusions
The maximum overall sugar recovery yields from the
bark-rich sawmill (a mixture of Hemlock hog fuel and
pin chips by 85% and 15%, respectively) were 13.6 g of
glucose (46% theoretical maximum), 10.5 g of mannose
and galactose (98% theoretical maximum), and 2.8 g of
xylose (85% theoretical maximum) out of 100 g of dry
raw feedstock. These results provide the basic informa-
tion for converting bark-rich softwood residues into
value-added products through enzyme and fermentation
processes.
References
Ballesteros, I., Oliva, J.M., Negro, M.J., Manzanares, P., Ballesteros,
M., 2002. Enzymic hydrolysis of steam exploded herbaceous
agricultural waste (Brassica carinata) at different particle sizes.
Process Biochem. 38, 187–192.
Bellamy, W.D., 1974. Single cell protein from cellulosic wastes.
Biotechnol. Bioeng. 26, 869–880.
Boussaid, A., Cai, Y., Robinson, J., Gregg, D.J., Nguyen, Q., Saddler,
J.N., 2001. Sugar recovery and fermentability of hemicellulose
hydrolysates from steam-exploded softwoods containing bark.
Biotechnol. Prog. 17, 887–892.
Chum, H.L., Johnson, D.K., Black, S.K., Overend, R.P., 1990.
Pretreatment-catalyst effects and the combined severity parameter.
Appl. Biochem. Biotechnol. 24–25, 1–14.
Curreli, N., Agelli, M., Pisu, B., Rescigno, A., Sanjust, E., Rinaldi, A.,
2002. Complete and efficient enzymic hydrolysis of pretreated
wheat straw. Process Biochem. 37, 937–941.
 K.H. Kim et al. / Bioresource Technology 96 (2005) 1249–1255
Esteghlalian, A., Hashimoto, A.G., Fenske, J.J., Penner, M.H., 1997.
Modeling and optimization of the dilute-sulfuric-acid pretreatment
of corn stover, poplar and switchgrass. Bioresour. Technol. 59,
129–136.
Harris, E.E., Beglinger, E., Hajny, G.J., Sherrard, E.C., 1945.
Hydrolysis of wood—treatment with sulfuric acid in a stationary
digester. Ind. Eng. Chem. 37, 12–23.
Holtzapple, M.T., Jun, J.-H., Ashok, G., Patibandla, S.L., Dale, B.E.,
1991. The ammonia freeze explosion (AFEX) process. Appl.
Biochem. Biotechnol. 28/29, 59–74.
Kim, K.H., Hong, J., 2001. Supercritical CO2 pretreatment of
lignocellulose enhances enzymatic cellulose hydrolysis. Bioresour.
Technol. 77, 139–144.
Kim, K.H., Tucker, M.P., Keller, F.A., Aden, A., Nguyen, Q.A., 2001.
Continuous countercurrent extraction of hemicellulose from pre-
treated wood residues. Appl. Biochem. Biotechnol. 91–93, 253–267.
Kim, K.H., Tucker, M.P., Nguyen, Q.A., 2002a. Effects of operating
parameters on countercurrent extraction of hemicellulosic sugars
from pretreated softwood. Appl. Biochem. Biotechnol. 98, 147–159.
Kim, K.H., Tucker, M.P., Nguyen, Q.A., 2002b. Effects of pressing
lignocellulosic biomass on sugar yield in two-stage dilute-acid
hydrolysis process. Biotechnol. Prog. 18, 489–494.
Lynd, L.R., Wyman, C.E., Gerngross, T.U., 1999. Biocommodity
engineering. Biotechnol. Prog. 15, 777–793.
1255
Mackie, K.L., Brownell, H.H., West, K.L., Saddler, J.N., 1985. Effect
of sulphur dioxide and sulphuric acid on steam explosion of
aspenwood. J. Wood Chem. Technol. 5, 405–425.
National Renewable Energy Laboratory, 2004. National Renewable
Energy Laboratory Standard Biomass Analytical Procedures.
Available from: <http://www.eere.energy.gov/biomass/analytical_
procedures.html>.
Nguyen, Q.A., Tucker, M.P., Boynton, B.L., Keller, F.A., Schell, D.J.,
1998. Dilute acid pretreatment of softwoods. Appl. Biochem.
Biotechnol. 70–72, 77–87.
Nguyen, Q.A., Tucker, M.P., Keller, F.A., Eddy, F.P., 2000. Two-
stage dilute-acid pretreatment of softwoods. Appl. Biochem.
Biotechnol. 84–86, 561–576.
Sherrard, E.C., Kressman, F.W., 1945. Review of processes in the
United States prior to World War II. Ind. Eng. Chem. 37, 5–8.
Soderstrom, J., Pilcher, L., Galbe, M., Zacchi, G., 2003. Two-step
steam pretreatment of softwood by dilute H2SO4 impregnation for
ethanol production. Biomass Bioenergy 24, 475–486.
Sudha, K., Rani, M., Swamy, V., Seenayya, G., 1998. Production of
ethanol from various pure and natural cellulosic biomass by
Clostridium thermocellum strains SS21 and SS22. Process Biochem.
33, 435–440.
Torget, R., Himmel, M.E., Grohmann, K., 1991. Dilute sulfuric acid
pretreatment of hardwood bark. Bioresour. Technol. 35, 239–246.