Biomass and Bioenergy 22 (2002) 401404

Optimizing acid-hydrolysis: a critical step for production of

ethanol from mixed wood chips
Jamshid Iranmahboob
a
, Farhad Nadim
a;
, Sharareh Monemi
b
a
The Environmental Research Institute, University of Connecticut, Route 44, Longley Building, 270 Middle Turnpike U-5210, Storrs,
CT 06269-5210, USA
b
The Department of Biomedical Engineering, University of Connecticut, 260 Glenbrook Rd., U-2157, Storrs, CT USA
Received 4 June 2001; received in revised form 10 December 2001; accepted 10 December 2001
Abstract
Ethanol can be produced from renewable lignocellulosic materials such as various types of natural woods. The cellulose
contents of wood can be converted to ethanol in a two-step process where acid-hydrolysis converts cellulose to glucose sugars
by hydrolysis (saccharication) and the resulting sugars can be converted to ethanol by fermentation. The main challenge of
producing fuel ethanol from renewable lignocellulosic biomass through acid-hydrolysis and fermentation is overcoming the
cost-limiting factors associated with various stages of this technology. In this study, sugar recovery rates from a mixture of
wood chips were investigated through three sets of acid-hydrolysis experiments. Wood chips were sorted to include equal
ratios (by weight) of softwood and hardwood. Acid concentration and the heating period were the two main factors aecting
dextrose yields. It was found that with the use of 26% by weight sulfuric acid, highest dextrose yields could be reached
within 2 h of heating time. This corresponds to overall conversion eciency of mixed wood chip cellulose to dextrose in
the range of 7882% based on theoretical values. ? 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Acid-hydrolysis; Biomass; Cellulose; Ethanol; Glucose; Lignin
1. Introduction
Advances in technology have allowed the conver-
sion of biomass into fuel ethanol as a potential source
of energy. Ethanol is a renewable energy source and
can be produced domestically in response to todays
high-energy demand. Due to environmental concerns,
the production of sugar fromagricultural waste materi-
als, forest residues and municipal solid wastes (MSW)

Corresponding author. Tel.: +1-860-486-6874; fax: +1-860-

486-5488.
E-mail addresses: jamshidim@hotmail.com (J. Iranmahboob),
fnadim@aqua.eri.uconn.edu (F. Nadim), monemi@nso2.uchc.edu
(S. Monemi).
and its subsequent conversion to biochemical fuel as
an alternative source of energy has gained substantial
grounds in the United States. These wastes may be
hydrolyzed by acids or enzymes to lower molecular
weight carbohydrates and nally to monomeric sug-
ars. The United States is the largest producer of wastes
in the world [2-kg (4:2 lb) per capita per day] [1]. In
terms of energy density, each ton of MSW is equiv-
alent to more than one barrel of oil. It has been esti-
mated that the cost of ethanol, with a feedstock cost
of $25=dry US ton will be reduced from its present
base of $1.16=gal to about $0.76 by the year 2015
(a reduction of 34%) [2].
Lignocellulosic materials such as agricultural, for-
est products (hardwood and softwood) and their
0961-9534/02/$ - see front matter ? 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0961- 9534( 02) 00016- 8
402 J. Iranmahboob et al. / Biomass and Bioenergy 22 (2002) 401404
residues are renewable resources of energy. Approxi-
mately 90% of the dry weight of most plant material is
stored in the form of cellulose, hemi-cellulose, pectin,
and lignin. Conversion of cellulose and hemi-cellulose
from waste materials to sugars provides a feedstock
for the production of fuel ethanol and will sub-
stantially reduce the amount of wastes that would
otherwise exert pressure on municipal landlls.
The main goal of this work was to investigate sugar
recovery rates from mixed wood chips originating
from a variety of sources with a view to develop an op-
timal and economically feasible system for production
of ethanol as a promising fuel and a base material for
other chemical products. The results of this study may
benet government and private sectors that are inter-
ested in the production of fuel and other by-product
chemicals from waste materials.
2. Hydrolysis
The complex structure of lignocellulose in plants
makes a primary protective barrier that prevents cell
destruction by bacteria and fungi. In order to break
down this structure for conversion of biomass to fuel
ethanol, the cellulose and hemi-cellulosic materials
must be broken down to corresponding monomers
(sugars) so that microorganism can utilize them.
There are three major hydrolysis processes for agricul-
tural and wood wastes to produce a variety of sugars
capable of making ethanol: dilute acid, concentrated
acid, and enzymatic hydrolysis [3,4]. Hemi-cellulose
is readily hydrolyzed by dilute acids under moderate
conditions, but much more extreme conditions are
needed for hydrolysis of cellulose. The main advan-
tage of the low concentration acid in the hydrolysis
process is that acid recovery may not be required
and there will be no signicant losses of acid. How-
ever, in a low concentrated acid process, the reaction
should be carried out at high temperature and pres-
sure, and due to poor yields of glucose from cellulose
in the hydrolysis step the ethanol yield is low. Due to
near-quantitative yield of glucose from cellulose, the
use of high concentration acid in the hydrolysis pro-
cess may yield higher quantities of ethanol but dier-
ent vessels and a good acid recovery process will be
required. The dilute acid-hydrolysis process uses high
temperatures (160

C) and pressures (10 atm) [5].

The acid concentration in the dilute acid-hydrolysis
process is in the range of 25% [6,4]. The acid
concentration used in concentrated acid-hydrolysis
process is in the range of 1030% [4]. Lower oper-
ating temperatures and pressures are required during
the concentrated acid-hydrolysis process. The con-
centrated acid-hydrolysis involves longer retention
times and results in higher ethanol yields than the
dilute acid-hydrolysis process [4]. Enzymes produced
by a variety of microorganisms are also capable of
breaking down lignocellulosic materials to sugars
in a longer retention time [7]. Enzymatic hydrolysis
requires feedstock pretreatment, enzyme production,
and enzyme recovery, which may make this option
economically unfeasible. Problems associated with the
hydrolysis process need more improvements in order
to reduce the operating cost for an ethanol-producing
plant that uses wood wastes as feedstock.
Development of a feasible process for the
acid-hydrolysis of wood chips that could lead high
sugar yields and result into less oxidation of the
produced dextrose by the concentrated acid were
investigated in three sets of bench-scale experiments.
3. Experimental procedure
Mixture of 50% hardwood (oak, birch and maple)
and 50% softwood (pine and cedar) chips free from
barks were dried at 72

C overnight. The wood chip

mixture was rechipped and sieved, and the fraction be-
tween 4 and 10 mm was used. Various lignocellulosic
raw materials composition for one class of hardwood
(populus) and one class of softwood (r) similar to
the wood chips used in this study are given in Table 1.
Dried, ground wood chips of 200 g were gradually
mixed with 500 g of 80% (by weight) H
2
SO
4
acid to
generate a homogeneous paste. The color of the paste
turned dark without resulting into severe oxidation of
the mixture by acid. Distilled boiling water of 500 g
was added to the paste to obtain a 33% (by weight)
acid mixed slurry and was stirred for 30 min at 100

C
using a water bath. The mixed slurry was then l-
trated. The ltration time, volume and weight of the
ltrate, and the weight of lter-cake were recorded.
The ltrate was then heated for 2 h. In order to mea-
sure the percent dextrose of the heated ltrate us-
ing a sugar analyzer (YSI 2700 SELECT) during the
J. Iranmahboob et al. / Biomass and Bioenergy 22 (2002) 401404 403
Table 1
Composition of various lignocellulosic raw materials in a typical
softwood and hardwood
Component Populus tristis Douglas r
(hardwood) (softwood)
Cellulose (wt%) 45.0 42.0
Hemi-cellulose (wt%) 30.0 27.0
Non-carbohydrate (%)
Lignin 20.0 28.3
Ash 1.0 0.2
Carbohydrate (% of sugar equivalent)
Glucose 40.0 50.0
Mannose 8.0 12.0
Galactose NA 1.3
Xylose 13.0 3.4
Arabinose 2.0 1.1
Source: Ref. [8].
heating process, samples were taken at 30 min inter-
vals and neutralized (pH: 68) with a 1 N NaOH solu-
tion. The same procedure was done for 26% and 20%
(by weight) acid mixture slurries.
4. Results and discussion
In the hydrolysis of wood wastes, the eective acid
concentration and the time of heating vary depending
on the composition of the wastes such as cellulose,
hemicellulose, lignin, ash and pectin. Wood wastes are
usually collected and stored as a mixture. Therefore,
in this study, acid-hydrolysis was mainly performed
on mixed wood chips. The results of hydrolysis of
mixed wood chips are shown in Table 2. The ltration
Table 2
The results for acid-hydrolysis of mixed wood chips
33% acid 26% acid 20% acid
Filtration time (95% by volume) 60 s 40 s 30 s
Filtrate volume 101 ml 122 ml 141 ml
Filtrate weight 130:6 g 147:7 g 164:4 g
Filter-cake weight 65 g 52 g 30 g
Dextrose of the mixed slurry (% by weight) 7.89 5.51 3.83
Dextrose of ltrate heated for 30 min (% by weight) 12.9 9.38 6.22
Dextrose of ltrate heated for 60 min (% by weight) 17.03 14.88 8.21
Dextrose of ltrate heated for 90 min (% by weight) 21.13 24.21 10.24
Dextrose of ltrate heated for 120 min (% by weight) 25.85 32.51 13.03
0
5
10
15
20
25
30
35
40
0 0.5 1 1.5 2 2.5
Time (hour)
%

D
e
x
t
r
o
s
e
20% H
2
SO
4
26% H
2
SO
4
33% H
2
SO
4
Fig. 1. The time sequence ltrate hydrolysis after treatment of
wood chips with sulfuric acid at dierent concentrations (samples
were taken at 30 min intervals). Data points are average values
of three experimental runs with error bars indicating the standard
error of the means.
time is longer for higher acid concentration because
of its high viscosity. The dextrose concentration of the
mixed slurry (after 30 min of heating process) was
highest for 33% acid slurry.
The results of heating process of the ltrates for
all three acid concentrations, 33%, 26%, and 20%
are shown in Fig. 1. The maximum dextrose (sugar)
concentration was achieved in 26% (by weight)
acid-hydrolysis process batch, in which ltrate was
heated for 2 h. Lignin is mostly insoluble in mineral
acids and only a small fraction of the lignin in a
biomass sample is solubilized during the hydrolysis
process [9]. With very small quantities of dissolved
lignin, the hydrolysis process of cellulose to sugar
becomes a simple process and can occur in a less
acid concentration mixture. However, at higher acid
404 J. Iranmahboob et al. / Biomass and Bioenergy 22 (2002) 401404
concentrations and heating times, cellulose may be de-
graded or oxidized during the heating process. There-
fore, optimizing acid concentration and the heating
time of the ltrate are principal factors of the hydro-
lysis process.
5. Conclusion
Cost-eective production of sugar from cellulose
and hemi-cellulosic material present in waste wood
chips through acid-hydrolysis is dependent on the con-
centration of acid and on the heating time of the l-
trate. The results of this study indicated that the use
of sulfuric acid at moderate concentrations (26% by
weight) and 2 h of heating time was able to produce
the highest yield of dextrose for the production of
ethanol. Further research is needed to make this pro-
cess economically feasible.
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