HEMICELLULOSE BIOREFINERY FOR

FURFURAL PRODUCTION: ENERGY

REQUIREMENT ANALYSIS AND MINIMIZATION
LUDOVIC MONTASTRUC*, OLUMOYE AJAO, MARIYA MARINOVA,
CATARINA BARRETO DO CARMO, SERGE DOMENECH

In recent years, the forest biorefinery has been identified and proposed as an opportunity for pulp and paper mills to improve their profitabil-
ABSTRACT

ity. The implementation of biorefinery units will have an impact on the energy requirements of the receptor mill, and the energy consumption
of the biorefinery should therefore be optimized before integration. The purpose of this work is to propose a biorefinery for the production
of furfural that can be integrated into a Kraft pulp mill. The operating conditions and the energy requirements of the biorefinery have been
determined. Analysis has shown that its energy consumption, although high, can be reduced. A mixed-integer non-linear programming
(MINLP) algorithm was used to minimize the energy requirements, and a new heat-exchanger network was developed that reduced the
steam requirement by 65% and the cooling water requirement by 82%.

INTRODUCTION
The pulp and paper industry has always
been a major sector of the Canadian econ-
omy; its healthy export rate has generated
significant contributions to the countrys
balance of payments. However, it has had
to face, over the last two decades, a world
market in transformation and a new eco-
nomic environment: competition from
new pulp-producing countries with a fast-
growing resource and low manufacturing
costs, a decline in the demand for commod-
ity products, and rising energy costs. The
industry has developed and is now imple-
menting a strategy to confront this situ-
ation and turn it into an advantage [1,2].
The cornerstone of this strategy is utiliza-
tion of the traditional feedstock of the in-
dustry, forest biomass, to manufacture new
value-added products by the application
of innovative transformative technologies.
This new vision of the manufacturing role
of the pulp and paper industry is often
referred to as the forest biorefinery by
analogy with the petro-chemical industry
[3]. However, this analogy does not take
into account one fundamental difference:
the forest biorefinery uses a renewable
feedstock with zero net carbon footprint,
while the petroleum refinery does not.
The specific objective of the work
presented herein was the extraction of a
class of wood component, the hemicellu-
loses, from wood chips upstream of the
pulping process and their conversion into
furfural, a high-market-value chemical
that can be used directly as an oil recov-
ery agent, pesticide, and nematicide or as
a precursor to many derivatives [4]. Some
of its principal derivatives are furfuryl

LUDOVIC MONTASTRUC SERGE DOMENECH OLUMOYE AJAO MARIYA MARINOVA CATARINA BARRETO
Universit de Toulouse, Universit de Toulouse, Department Department DO CARMO
Laboratoire de Gnie Laboratoire de Gnie of Chemical of Chemical Department of
Chimique, U.M.R. 5503 Chimique, U.M.R. 5503 Engineering, Engineering, Chemical Engineering,
CNRS/INP/UPS, CNRS/INP/UPS, cole Polytechnique cole Polytechnique cole Polytechnique
France France de Montral, de Montral, de Montral,
*Contact: ludovic.montastruc@ensiacet.fr Montral, Qc Montral, Qc Montral, Qc
Canada Canada Canada

48 J-FOR Journal of Science & Technology for Forest Products and Processes: VOL.1, NO.3, 2011

alcohol, which is used for making foundry
resins, furan, furoic acid, and furfurylam-
ine [5]. The extraction and conversion
process would be constructed on the site
of a Kraft mill manufacturing pulp for
papermaking and would be intensively in-
tegrated with the Kraft process from the
energy and material standpoints. For the
purpose of this case study, the three-step
hemicellulose extraction and conversion
process is composed of technologies that
have been proven to the large pilot-plant
or demonstration stages and that could
be implemented in a reasonably short
time [4,6]. The hemicellulose biorefinery
should be optimized from the standpoint
of energy demand (steam and water) so
that it does not increase the overall fossil-
fuel consumption of the site. The analy-
sis was supported by a process simulation
model constructed using the Aspen Plus
software. A mixed-integer non-linear pro-
gramming (MILNP) algorithm was used
to minimize the energy requirement and
generate the corresponding heat-exchang-
er network.
HEMICELLULOSE EXTRACTION
AND CONVERSION PROCESS
The biorefinery can be implemented in
Fig. 1 - Process diagram of the hemicellulose biorefinery.
J-FOR
three main steps: hemicellulose extraction
with hot water and hydrolysis, conversion
in a low-pH chemical reaction of C5 sugars
into furfural, and purification of furfural
by azeotropic distillation (Fig. 1).The key
pieces of equipment are labelled using
the prefixes HX (heat exchanger), DEC
(decanter), R (reactor), DIST (distillation
column), COND (condenser), and REB
(reboiler). To assess the opportunities for
energy integration within the biorefinery, a
process simulation of the furfural biorefin-
ery was first carried out using the commer-
cially available Aspen Plus software (Fig.
1). The physical property data for many
of the key non-conventional solids used
in the simulation of the furfural process
are not in the softwares standard property
database. These properties were obtained
from the National Renewable Energy
Laboratory (NREL) physical property da-
tabase for bio-fuel components [7].
The three main steps in the biorefin-
ery implementation are discussed in detail
below.
Hemicellulose Extraction
Hemicelluloses are polymers consisting of
C6 sugars (mannose, glucose, and galac-
tose) and C5 sugars (xylose and arabinose).
Journal of Science & Technology for Forest Products and Processes: VOL.1, NO.3, 2011
SPECIAL BIOREFINERY ISSUE
During hydrolysis, the polymers are solu-
bilized to yield monomeric pentoses and
hexoses. Three methods that have been
used at laboratory scale for the hydrolysis
of hemicelluloses from wood chips before
pulping were considered. They involve
hydrolysis with a dilute acid (H2SO4), us-
ing hot water, or using an alkaline solution
(NaOH). The percentages of the main
wood components that can be extracted
using each method were based on data
from the literature [6,8,9]. As shown in
Table 1, the use of sodium hydroxide re-
sults in a slightly lower percentage of ex-
tracted hemicelluloses. More importantly,
the conversion of pentoses to furfural
requires a low pH (<1) [8]. Therefore, ex-
traction with dilute acid or with hot water
is a more suitable method. Hot-water ex-
traction has an advantage over the use of
H2SO4 because it does not require expen-
sive corrosion-resistant materials [10].
The extraction stage was therefore
modelled based on the use of hot water.
TABLE 1 Components extracted by different methods.
Hemicelluloses Cellulose Lignin
(%) (%) (%)
H2SO4 16.0 0.6 3.5
NaOH 14.3 - 6.54
Hot water 15 2.0 2.0
49
The extraction conditions and the con-
centrations of dissolved hemicelluloses
in the hydrolysate (pentoses and hexoses)
are given in Table 2. Prolonged hydroly-
sis leads to the dissolution of cellulose in
the hydrolysate, but this can be limited
by not extracting more than 15% of the
hemicelluloses. The combustibility of the
black liquor is not significantly degraded
because the hemicelluloses have a low
heating value.
Extraction conditions and hydrolysate
TABLE 2
composition using hot-water hydrolysis.
Temperature (C)
Pressure (kPa)
Monomeric pentose in hydrolysate (g/L)
Monomeric hexose in hydrolysate (g/L)
Energy requirement (GJ/ODT chips)
Hemicellulose Conversion
In the conversion step, the pentoses are
converted into furfural through dehydra-
tion. This can be carried out by means of
several commercial processes. The older
processes have a lower yield compared to
newer processes that are already at the pi-
lot-plant scale. An overview of the operat-
ing conditions of some furfural production
processes, based on reviews by de Jong et
al. [11] and Zeitsch [4], is provided in Table
3 and discussed briefly below. The batch
process is a low-cost process developed in
China. Its yield is about the same as that
of the Quaker Oats batch process, which
is the oldest furfural-making process. The
continuous process is an improvement to
the batch process by Quaker Oats, but has
a shorter residence time. The Supratherm
process is patented by a German company
and operates at a higher temperature than
the older processes. The Vedernikov pro-
cess originated in Latvia and is one of the
first processes with yields as high as 75%.
All the processes were considered for se-
lecting the operating conditions for the
case study. The operating condition se-
lected for the conversion process lie with-
in the range of several processes that are
already at the pilot-plant stage. The yield
for the case study is 75%. The residence
time in the reactor is shortened at high
temperatures and pressures. The output
of the conversion process is a mixture of
furfural and water (3% (wt.) of furfural).
23
50 J-FOR Journal of Science & Technology for Forest Products and Processes: VOL.1, NO.3, 2011
Furfural Purification
Furfural forms an azeotrope with water;
the azeotropic point is 35% by weight of
furfural. The boiling point of furfural is
161.7C at 1 atm, while that of the azeo-
trope is 97.85C. All known processes for
converting pentoses to furfural produce a
stream consisting of up to 6% of furfural
and more than 90% of water by weight,
which is below the azeotropic point [4].
The conventional azeotropic distillation
method was selected for the purification
of the furfural-water mixture. In the first
170
distillation column, a mixture of approxi-
800
mately 30% by weight of furfural is ob-
10.8
tained as the distillate. This is cooled and
2.9
0.8 fed into a decanter, where it separates
spontaneously into a furfural-lean and a
furfural-rich mixture. The use of decanters
for liquid-liquid extraction is possible be-
cause of the limited solubility of furfural
in water (8.3 wt% at 20C). Furfural at
99% purity is obtained by distillation of
the furfural-rich mixture.
ENERGY ANALYSIS AND SITE INTE-
GRATION
The receptor mill for the biorefinery is a
Kraft pulp mill that produces 1000 t/d
bleached Kraft pulp from hardwood feed-
Fig. 2 - Energy requirements for the biorefinery.
TABLE 3 Some conversion processes for the production of furfural.
Batch Process
Temperature, C 140180
Pressure, atm 6 ~10
Residence time, h ~5
Yield, % 3550
Status Commercialized Commercialized
stock (a mix of aspen, maple, and birch
wood chips). To achieve an integrated
biorefinery, the receptor mill should be
able to supply the energy and material
requirements of the biorefinery process
without increasing the fossil-fuel con-
sumption of the site. The material and
energy integration between the Kraft pro-
cess and the biorefinery is depicted in Fig.
2. The extraction step requires that water
be heated and pressurized from 2C /
101 kPa to 170C / 1200 kPa to satisfy
the extraction conditions in the reactor
(R-01) after mixing with the wood chips.
Direct injection of steam (19 MW) is also
required for the extraction stage. Approxi-
mately 34 MW steam can be recovered
by flash separation (FLSH-01) before the
conversion stage. The conversion stage
(R-02 and HX-03) has the lowest ener-
gy demand of the three steps. The total
amount of recoverable energy is approxi-
mately 40 MW. The energy requirement is
enormous, and it is therefore important to
minimize the energy demand of the biore-
finery before integration. The recoverable
energy is available at different conditions,
and therefore the locations at which it can
be reused are limited.
Quaker Oats Supratherm Vedernikov Case Study
- 200240 - 170210
2030 - 1822
~1 Very short - -
~ 55 ~70 ~ 75 ~ 75
Pilot Plant Pilot Plant -
 SPECIAL BIOREFINERY ISSUE

TABLE 4 Data for the biorenery heat exchangers. network by providing the following: utili-
Equipment
Mass Flow Tin Tout Duty Area Total Cost ties required, stream matches and number
(kg/s) (C) (C) (kW) (m2) (k$/y)
of units, heat loads and operating temper-
HX-01 62.99 2.0 170.0 46,772 858 2,500
atures of each exchanger, network config-
HX-02 13.37 170.0 20.0 34,710 885 681
uration and flows for all branches, and the
HX-03 9.15 170.0 98.0 3,093 30 61
area of each exchanger.
HX-04 0.94 97.2 50.0 163 4 3
Yee and Grossmann (1990) proposed
HX-05 8.93 99.8 20.0 2853 59 57 a stage-wise superstructure representation
HX-06 0.25 50.0 98.0 25 3 22 for the simultaneous HEN synthesis prob-
HX-07 0.22 160.0 20.0 350 1 2 lem. At each stage, hot and cold streams
COND-01 0.94 97.3 97.2 5,611 64 108 are split to enable the potential existence
REB-01 8.93 99.9 99.8 5,810 62 311 of a heat exchanger to match any hot-cold
COND-02 0.02 97.4 97.3 104 3 3 pair of streams. This concept enables the
EB-02 0.23 100.0 99.0 139 2 8 implicit inclusion of a large number of
1971 3,800 system topologies. Before a stream enters
a new stage, the streams from the preced-
The data generated for the heat ex- the implementation of the furfural biore- ing stage are re-mixed isothermally. Ex-
changers in the biorefinery base case are finery feasible from the energy standpoint treme utilities are assumed to be placed at
summarized in Table 4. For each heat ex- and economically viable. The focal points the outlets of the superstructure.
changer, the heat duty, area, and cost of for the heat-network optimization are the To solve the MINLP problem, the
the equipment as well as the heating and pieces of equipment with large surface COUENNE (GAMS) software was used.
cooling demands are given. areas and high heat requirements, such as COUENNE (convex over- and under-
The capacity and dimensions of the the re-boilers and condensers of the distil- envelopes for non-linear estimation) is an
equipment were calculated using Aspen lation columns and the heat exchangers. open-source solver for non-convex mixed-
Process Economic Analyzer. A plausi- The algorithm used in this work is integer non-linear programs (MINLPs).
bility verification was made by means of based on the MINLP [14]. The heat-ex- The code was developed originally by a
cost functions and charts [12]. The cal- changer network (HEN) synthesis prob- collaboration of Carnegie Mellon Uni-
culated costs were adjusted for inflation lem addressed in this paper can be stated versity and IBM Research. COUENNE
using chemical engineering indices. The as follows: solves convex and non-convex MINLPs
process data for the steam and cold water A set of hot process streams H using an LP-based spatial branch-and-
consumed by the biorefinery are given in to be cooled and a set of cold process bound algorithm [15].
Table 5. streams C to be heated are given. Each The process specifications of the
The costs of steam produced in a hot and cold streams heat capacity, streams and the cost ratios of the network
biomass boiler (3.3$/t) and that of fresh flow rate, and initial and target tem- are given in Tables 4 and 5.
water (0.065$/m3) were obtained from the peratures (stated as either exact values
literature [13]. or inequalities) are also specified. HEAT-EXCHANGER NETWORK
Furfural production of 7,000 t/yr A set of hot utilities HU and a The optimal point was found to be 1.2
can be achieved in the biorefinery by ex- set of cold utilities CU with their cor- M$/yr. Without energy integration, the to-
tracting 15% of the hemicellulose content responding temperatures are given. tal cost is about 3.8 M$/yr. The exchanger
of the wood. area is approximately 1971 m2 without
The term utilities for the biorefin- integration; with integration, this value in-
MINIMIZATION OF ENERGY CON- ery refers to the steam and cold-water re- creases to 2861 m2. The steam consump-
SUMPTION quirements that are obtained on-site from tion decreases by approximately 65% with
The purpose of energy consumption min- the Kraft process. energy integration, while the cooling wa-
imization is to reduce the energy require- The objective is then to determine ter requirement is reduced by 82%. Each
ments that must be met by the receptor the heat-exchanger network with the low- heat exchanger is characterized by the
Kraft pulp mill. This is necessary to make est annual cost. The solution defines the exchanger area and the exchanger power.
The minimum temperature difference be-
TABLE 5 Process data for steam and cold water consumption. tween the cold flow and the hot flow is
Tin (C) Tout (C)
approximately 5C. The optimized heat-
Cost ($.kW-1.year-1) h (kW.m-2.K-1) Current name
exchanger network contains 15 heat ex-
Steam 200 170 53.5 2.5 HU
changers in total (Fig. 3). The cost of steam
Cold water 2 30 19.3 1 CU
makes up 83% of the optimum total cost.

J-FOR Journal of Science & Technology for Forest Products and Processes: VOL.1, NO.3, 2011 51
CONCLUSIONS
A biorefinery for the production of 7,000
t/y furfural from hemicelluloses extracted
from a Kraft pulping process has been
developed and simulated. The process is
technically feasible, and its integration po-
tential has been enhanced by minimizing
its energy requirement. The optimized
biorefinery heat-exchanger network was
developed using a mixed-integer non-lin-
ear programming (MINLP) algorithm. Af-
ter minimization, it was possible to achieve
a cost reduction of 68% per annum. The
significance of energy integration and how
a resulting decrease in cost can contribute
to making the process more attractive eco-
nomically have also been demonstrated.
ACKNOWLEDGMENTS
This work was supported by a grant from
Fig. 3 - Optimal Heat-Exchanger Network.
23
52 J-FOR Journal of Science & Technology for Forest Products and Processes: VOL.1, NO.3, 2011
the R&D Cooperative Program of the
National Science and Engineering Re-
search Council of Canada. The industrial
partners of this project are gratefully ac-
knowledged for their help. The authors
would like to thank Professor Jean Paris
form cole Polytechnique for his com-
ments and advices during the develop-
ment of this work.
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