HEMICELLULOSE BIOREFINERY FOR

FURFURAL PRODUCTION: ENERGY

REQUIREMENT ANALYSIS AND MINIMIZATION
ABSTRACT

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 profitability. 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 economy; 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 economic environment: competition from
new pulp-producing countries with a fastgrowing resource and low manufacturing
costs, a decline in the demand for commodity products, and rising energy costs. The
industry has developed and is now imple-

LUDOVIC MONTASTRUC

menting a strategy to confront this situation and turn it into an advantage [1,2].
The cornerstone of this strategy is utilization of the traditional feedstock of the industry, 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:

SERGE DOMENECH
Universit de Toulouse,
Universit de Toulouse,
Laboratoire de Gnie
Laboratoire de Gnie
Chimique, U.M.R. 5503
Chimique, U.M.R. 5503
CNRS/INP/UPS,
CNRS/INP/UPS,
France
France
*Contact: ludovic.montastruc@ensiacet.fr

48

J-FOR

OLUMOYE AJAO

Department
of Chemical
Engineering,
cole Polytechnique
de Montral,
Montral, Qc
Canada

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 hemicelluloses, 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 recovery agent, pesticide, and nematicide or as
a precursor to many derivatives [4]. Some
of its principal derivatives are furfuryl

MARIYA MARINOVA

Department
of Chemical
Engineering,
cole Polytechnique
de Montral,
Montral, Qc
Canada

Journal of Science & Technology for Forest Products and Processes: VOL.1, NO.3, 2011

CATARINA BARRETO
DO CARMO

Department of
Chemical Engineering,
cole Polytechnique
de Montral,
Montral, Qc
Canada

SPECIAL BIOREFINERY ISSUE

alcohol, which is used for making foundry

resins, furan, furoic acid, and furfurylamine [5]. The extraction and conversion
process would be constructed on the site
of a Kraft mill manufacturing pulp for
papermaking and would be intensively integrated 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 fossilfuel consumption of the site. The analysis was supported by a process simulation
model constructed using the Aspen Plus
software. A mixed-integer non-linear programming (MILNP) algorithm was used
to minimize the energy requirement and
generate the corresponding heat-exchanger network.
HEMICELLULOSE
EXTRACTION
AND CONVERSION PROCESS

The biorefinery can be implemented in

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 biorefinery was first carried out using the commercially 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 database for bio-fuel components [7].
The three main steps in the biorefinery implementation are discussed in detail
below.

During hydrolysis, the polymers are solubilized 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), using 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 results in a slightly lower percentage of extracted hemicelluloses. More importantly,
the conversion of pentoses to furfural
requires a low pH (<1) [8]. Therefore, extraction with dilute acid or with hot water
is a more suitable method. Hot-water extraction has an advantage over the use of
H2SO4 because it does not require expensive 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
(%)

H2SO4

16.0

0.6

3.5

NaOH

14.3

6.54

15

2.0

2.0

Hemicellulose Extraction

Hemicelluloses are polymers consisting of

C6 sugars (mannose, glucose, and galactose) and C5 sugars (xylose and arabinose).

Hot water

Lignin
(%)

Fig. 1 - Process diagram of the hemicellulose biorefinery.

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Journal of Science & Technology for Forest Products and Processes: VOL.1, NO.3, 2011

49

The extraction conditions and the concentrations of dissolved hemicelluloses

in the hydrolysate (pentoses and hexoses)
are given in Table 2. Prolonged hydrolysis 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.
TABLE 2

Extraction conditions and hydrolysate

composition using hot-water hydrolysis.
Temperature (C)

170

Pressure (kPa)

800

Monomeric pentose in hydrolysate (g/L)

Monomeric hexose in hydrolysate (g/L)

10.8
2.9

Energy requirement (GJ/ODT chips)

0.8

Hemicellulose Conversion

In the conversion step, the pentoses are

converted into furfural through dehydration. 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 pilot-plant scale. An overview of the operating 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 process originated in Latvia and is one of the
first processes with yields as high as 75%.
All the processes were considered for selecting the operating conditions for the
case study. The operating condition selected for the conversion process lie within 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

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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 azeotrope 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
distillation column, a mixture of approximately 30% by weight of furfural is obtained as the distillate. This is cooled and
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 because 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 INTEGRATION

The receptor mill for the biorefinery is a

Kraft pulp mill that produces 1000 t/d
bleached Kraft pulp from hardwood feed-

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 consumption of the site. The material and
energy integration between the Kraft process 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. Approximately 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 energy demand of the three steps. The total
amount of recoverable energy is approximately 40 MW. The energy requirement is
enormous, and it is therefore important to
minimize the energy demand of the biorefinery before integration. The recoverable
energy is available at different conditions,
and therefore the locations at which it can
be reused are limited.

Fig. 2 - Energy requirements for the biorefinery.

TABLE 3

Some conversion processes for the production of furfural.

Batch Process

Quaker Oats

Supratherm

Vedernikov

Case Study

Temperature, C

140180

200240

170210

Pressure, atm

~10

2030

1822

Residence time, h

~5

~1

Very short

Yield, %

3550

~ 55

~70

~ 75

~ 75

Status

Commercialized

Commercialized

Pilot Plant

Pilot Plant

Journal of Science & Technology for Forest Products and Processes: VOL.1, NO.3, 2011

SPECIAL BIOREFINERY ISSUE

TABLE 4

Equipment

Mass Flow
(kg/s)

Data for the biorenery heat exchangers.

Tin
(C)

Tout
(C)

Duty
(kW)

Area
(m2)

Total Cost
(k$/y)

HX-01

62.99

2.0

170.0

46,772

858

2,500

HX-02

13.37

170.0

20.0

34,710

885

681

HX-03

9.15

170.0

98.0

3,093

30

61

HX-04

0.94

97.2

50.0

163

HX-05

8.93

99.8

20.0

2853

59

57

HX-06

0.25

50.0

98.0

25

22

HX-07

0.22

160.0

20.0

350

COND-01

0.94

97.3

97.2

5,611

64

108
311

REB-01

8.93

99.9

99.8

5,810

62

COND-02

0.02

97.4

97.3

104

EB-02

0.23

100.0

99.0

139

1971

3,800

The data generated for the heat exchangers in the biorefinery base case are
summarized in Table 4. For each heat exchanger, the heat duty, area, and cost of
the equipment as well as the heating and
cooling demands are given.
The capacity and dimensions of the
equipment were calculated using Aspen
Process Economic Analyzer. A plausibility verification was made by means of
cost functions and charts [12]. The calculated costs were adjusted for inflation
using chemical engineering indices. The
process data for the steam and cold water
consumed by the biorefinery are given in
Table 5.
The costs of steam produced in a
biomass boiler (3.3$/t) and that of fresh
water (0.065$/m3) were obtained from the
literature [13].
Furfural production of 7,000 t/yr
can be achieved in the biorefinery by extracting 15% of the hemicellulose content
of the wood.
MINIMIZATION OF ENERGY CONSUMPTION

The purpose of energy consumption minimization is to reduce the energy requirements that must be met by the receptor
Kraft pulp mill. This is necessary to make
TABLE 5

Steam
Cold water

the implementation of the furfural biorefinery feasible from the energy standpoint
and economically viable. The focal points
for the heat-network optimization are the
pieces of equipment with large surface
areas and high heat requirements, such as
the re-boilers and condensers of the distillation columns and the heat exchangers.
The algorithm used in this work is
based on the MINLP [14]. The heat-exchanger network (HEN) synthesis problem addressed in this paper can be stated
as follows:
A set of hot process streams H
to be cooled and a set of cold process
streams C to be heated are given. Each
hot and cold streams heat capacity,
flow rate, and initial and target temperatures (stated as either exact values
or inequalities) are also specified.
A set of hot utilities HU and a
set of cold utilities CU with their corresponding temperatures are given.
The term utilities for the biorefinery refers to the steam and cold-water requirements that are obtained on-site from
the Kraft process.
The objective is then to determine
the heat-exchanger network with the lowest annual cost. The solution defines the

Process data for steam and cold water consumption.

Tin (C)

Tout (C)

200

170

53.5

2.5

HU

30

19.3

CU

J-FOR

Cost ($.kW-1.year-1) h (kW.m-2.K-1) Current name

network by providing the following: utilities required, stream matches and number
of units, heat loads and operating temperatures of each exchanger, network configuration and flows for all branches, and the
area of each exchanger.
Yee and Grossmann (1990) proposed
a stage-wise superstructure representation
for the simultaneous HEN synthesis problem. At each stage, hot and cold streams
are split to enable the potential existence
of a heat exchanger to match any hot-cold
pair of streams. This concept enables the
implicit inclusion of a large number of
system topologies. Before a stream enters
a new stage, the streams from the preceding stage are re-mixed isothermally. Extreme utilities are assumed to be placed at
the outlets of the superstructure.
To solve the MINLP problem, the
COUENNE (GAMS) software was used.
COUENNE (convex over- and underenvelopes for non-linear estimation) is an
open-source solver for non-convex mixedinteger non-linear programs (MINLPs).
The code was developed originally by a
collaboration of Carnegie Mellon University and IBM Research. COUENNE
solves convex and non-convex MINLPs
using an LP-based spatial branch-andbound algorithm [15].
The process specifications of the
streams and the cost ratios of the network
are given in Tables 4 and 5.
HEAT-EXCHANGER NETWORK

The optimal point was found to be 1.2

M$/yr. Without energy integration, the total cost is about 3.8 M$/yr. The exchanger
area is approximately 1971 m2 without
integration; with integration, this value increases to 2861 m2. The steam consumption decreases by approximately 65% with
energy integration, while the cooling water requirement is reduced by 82%. Each
heat exchanger is characterized by the
exchanger area and the exchanger power.
The minimum temperature difference between the cold flow and the hot flow is
approximately 5C. The optimized heatexchanger network contains 15 heat exchangers in total (Fig. 3). The cost of steam
makes up 83% of the optimum total cost.

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 potential has been enhanced by minimizing
its energy requirement. The optimized
biorefinery heat-exchanger network was
developed using a mixed-integer non-linear programming (MINLP) algorithm. After 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 economically have also been demonstrated.
ACKNOWLEDGMENTS

This work was supported by a grant from

the R&D Cooperative Program of the

National Science and Engineering Research Council of Canada. The industrial
partners of this project are gratefully acknowledged for their help. The authors
would like to thank Professor Jean Paris
form cole Polytechnique for his comments and advices during the development of this work.
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Fig. 3 - Optimal Heat-Exchanger Network.

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