Memorias del XXXIV Encuentro Nacional y III Congreso Internacional de la AMIDIQ

7 al 10 de mayo de 2013, Mazatlán, Sinaloa, México

XYLITOL AND BIOETHANOL PRODUCTION FROM LIGNOCELLULOSES: A

SYSTEMATIC MODEL-BASED SIMULATION FOR A BIOREFINERY PROCESS
EVALUATION

Ricardo Morales-Rodrigueza*, Divanery Rodriguez-Gomezb, Merlín Alvarado-Moralesc, Helen Denise Lugo-

Mendeza, José Antonio de los Reyes-Herediaa, Eduardo Salvador Perez-Cisneros a
a
Departamento de Ingeniería de Procesos e Hidráulica, Universidad Autónoma Metropolitana-Iztapalapa, Av.
San Rafael Atlixco 186, C.P. 09340, México, D.F., MÉXICO. *e-mail: rmro@xanum.uam.mx
b
Departamento de Biotecnología, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco
186, C.P. 09340, México, D.F., MÉXICO.
c
Departament of Environmental Engineering, Technical University of Denmark. DK-2800 Kgs. Lyngby,
DENMARK.

Abstract
This study presents a model-based evaluation for the combined production of bioethanol
and xylitol from agroindustrial residues aiming to construct a biorefinery modelling
platform. Firstly, the addition of the xylitol production section was added to four process
configurations for bioethanol production. In order to select the best process configuration,
bioethanol and xylitol profit was selected as benchmarking criteria (USD). The results
show that the configuration having a simultaneous saccharification and co-fermentation
operating in continuous with recycle of the unreacted solid (SSCF-C_RECY) with xylitol
production had 25.1% more income than the reference process configuration (SSCF-C). For
the inclusion of the xylitol process configuration to the original bioethanol production
process, an analysis about the correct position of the xylitol reactor was done. This study
also allowed the analysis of the possibility of having the production of high value-added
product such as xylitol.
Introduction
According to The European commission predictions, 20% of the transportation fuel and
25% of chemicals should be produced from biomass by 2030 [1]. Therefore, continued
research on developing production processes for conversion of biomass into biofuels and
added-value bioproducts, such as xylitol, is being conducted [2]. Xylitol is a five-carbon
sugar alcohol used for prevention of dental caries and acute otitis media in small children. It
is also extensively used as sweetener. In 2007, the annual production was between 20,000
and 40,000 ton per year with an estimated market value of 40–80  M€ [3].
Industrially, xylitol is produced by reducing pure xylose, obtained from hardwood
hydrolysates, in the presence of a Raney nickel catalyst [4]. Recently, the biotechnological
production of xylitol has reached importance due to this is produced by yeast metabolism,
where Candida strains has become important over Saccharomyces cerevisiae by being a
natural D-xylose consumer and maintaining the reduction–oxidation balance during xylitol
accumulation. Up to now, the process design has been mostly done by experimental
approach, which can be expensive from the economical and time consuming perspective [5,
6]. Thus, a systematic model-based simulation could be an option to analyze the production
process from the economical and feasibility point of view.
Previously, Morales-Rodriguez et al. [7] presented a dynamic model-based approach for
second generation (2G) bioethanol production, developing a Dynamic Lignocellulosic
Bioethanol (DLB 1.0) modeling platform, which allowed performing quantitative
simulations. The DLB 1.0 was already extended adding the dynamic modelling of the
downstream processes (distillation and molecular sieve units) and the employed heat

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© 2013 Academia Mexicana de Investigación y Docencia en Ingeniería Química (AMIDIQ)
ISBN: 978-607-95593-1-1
 Memorias del XXXIV Encuentro Nacional y III Congreso Internacional de la AMIDIQ
7 al 10 de mayo de 2013, Mazatlán, Sinaloa, México

exchangers in the process [8]. However, these studies did not include the conversion of
xylose into xylitol in the process route, which can be strategically added to the modeling
platform since glucose and xylose are still present in the waste stream of the process.
Therefore, the objective of this study was to present an extension of the DLB 1.0 model
platform by the addition of the dynamic modeling for the conversion of xylose into xylitol.
The comparison of selected process configurations and operations was carried out based on
the combined production cost for bioethanol ($USD/gal-ethanol) and xylitol ($USD/gal-
xylitol). This study allowed deciding from an economical point of view on the introduction
of a xylitol production section in the original bioethanol production process, moreover,
showing and analyzing the reliability of having a biorefinery platform by including xylitol
production into the process.
Xylitol mathematical model and production pathway
The mathematical model employed in this work was taken from a previous work proposed
by Tochampa et al. [5], which considers the biomass growth rate, the rate of glucose and
xylose uptake related with biomass concentration and the production rate of intracellular
and extracellular xylitol. Moreover, the original model for xylitol production considers a
reactor operating in batch, therefore, the model was extended for a continuous operation
mode, considering the residence time with higher xylitol production.
As far as the biochemical pathway to produce xylitol from xylose is concerned, it can be
described as follows: once xylose is inside the cell, it is reduced to xylitol by the enzyme
xylose reductase in a step that consumes NADPH (reducing agent). Part of the xylitol
produced is excreted and the rest is converted to xylulose through the action of NAD+-
dependent xylitol dehydrogenase (to regenerate NADPH). Xylulose is further metabolized
to generate cell mass and maintenance energy. In the presence of an easily metabolized
carbon source, such as glucose, the cell can generate energy and biomass directly from
glucose via glucose-6-phosphate (Glu-6P); consequently, the hexose monophosphate
pathway for producing Glu-6P from xylulose via xylulose-5-phosphate (used in absence of
glucose) slows down. This reduces the consumption of xylitol within the cell and more of it
can be excreted [5]. Supplementation with glucose in xylose fermentation can thus be used
to enhance the yield of xylitol, however, high concentrations of glucose are known to
inhibit xylose transport into the cell and repress induction of relevant enzymes by xylose
[6].
Towards a biorefinery structure: addition of the xylitol production section to the
extended version of the dynamic lignocellulosic bioethanol 1.0 model platform
A xylitol production section was added to the previous extended version [8] of the DLB 1.0
model platform [7], consisting on adding a heat exchanger to reach the temperature of
30°C, followed by the xylitol reactor converting the remaining xylose contents in the
bottom stream of both distillation columns (illustrated in Figure 1). The addition of
production of a high valued-added product from the waste streams of the bioethanol
production process represents an opportunity for evaluating a biorefinery platform.
It is known that the xylitol production by yeast can be affected by several factors such as,
culture conditions, initial xylose concentration, and the presence of inhibitor compounds in
the hemicellulosic hydrolysates. In the substrate concentration process, several inhibitors
such as glucose, acetic acid, furfural, 5-hydroxymethylfurfural (HFM) and phenolic
compounds released by acid hydrolysis can be obtained together with xylose. These
undesirable inhibitory by-products can severely impair the fermentative process by
inhibiting microbial growth and metabolism [9]. On the other hand, to the best of our

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© 2013 Academia Mexicana de Investigación y Docencia en Ingeniería Química (AMIDIQ)
ISBN: 978-607-95593-1-1
 Memorias del XXXIV Encuentro Nacional y III Congreso Internacional de la AMIDIQ
7 al 10 de mayo de 2013, Mazatlán, Sinaloa, México

knowledge, the inhibition effect of ethanol on Candida genus has not been completely
studied and none available information was found. Thereby, for the sake of the process
design, the xylitol production section was added after ethanol was eliminated from process
streams.

Figure 1. Scheme of the addition of the xylitol production section to the extended version of the DLB 1.0

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© 2013 Academia Mexicana de Investigación y Docencia en Ingeniería Química (AMIDIQ)
ISBN: 978-607-95593-1-1
 Memorias del XXXIV Encuentro Nacional y III Congreso Internacional de la AMIDIQ
7 al 10 de mayo de 2013, Mazatlán, Sinaloa, México

The extended process configurations are the following: a) separate enzymatic hydrolysis
operating in continuous-recycle and co-fermentation reactor in continuous (C_RECY-C); b)
separate enzymatic hydrolysis and co-fermentation both having an operation in continuous-
recycle (C_RECY-C_RECY); c) simultaneous saccharification and co-fermentation
operating in continuous (SSCF-C) and d) simultaneous saccharification and co-
fermentation operating in continuous with recycle of unreacted insoluble solids (SSCF_C-
RECY). The model implementation and the simulations were performed using Matlab (The
Mathworks, Natick, Massachusetts).
Benchmarking criteria for the comparison of the extended process models
The extended process models were compared employing the production costs for
bioethanol and xylitol as the benchmarking criteria. The production costs considered were:
Feedstock, utilities (low-pressure steam, high-pressure steam and cooling water) and
additives (enzyme loading in the enzymatic hydrolysis and sulfuric acid loading in the
pretreatment) employed in the production to achieve the desired process conditions. The
production cost for ethanol was calculated according to the equation (1) and xylitol
production cost was calculated using equation (2). Notice that only utilities cost (cooling
water) is considered for xylitol production, since after the distillation columns the
temperature at the waste streams must be decreased to carry out the fermentation of xylose
into xylitol. The cost information data are shown in Table 1.
USD
Pr oduction _ Cost _ Ethanol  cFeedstock  cutilities  c Additives  (1)
gal  ethanol
USD
Pr oduction _ Cost _ Xylitol  cutilities  (2)
gal  xylitol
where CFeedstock , CUtilities and CAdditives represent the cost of the feedstock, utilities and
additives, respectively.

Table 1. Cost of the considered characteristics of the bioethanol production process [10, 11].
Considered characteristics of the process Cost (USD/kg)
Feedstock cFeedstock Corn stover 0.03
Utilities cUtilities Low-pressure steam 0.0075
High-pressure steam 0.0094
Cooling water 0.0002
Additives cAdditives Sulfuric acid 0.085
Enzymes 1.85
Results
Table 2 illustrates the results obtained for the bioethanol and xylitol production cost in the
extended version [8] of the DLB 1.0 and the potential profit for xylitol production for
certain period of operation (14.5 days). The last means that the potential incomes whether
the xylitol would be totally purified where only expenses for cooling water were subtracted,
while no cost for the purification process was deducted. The commercial cost employed for
calculating profit for bioethanol was 2.5 USD/gal-ethanol [12], while the price of the
potential profit for the produced xylitol was 3 USD/kg-xylitol [13]. Albeit, the prices for
bioethanol and xylitol have some uncertainty, they were selected with the aim of making a
fair comparison among the analyzed process configurations.
The SSCF-C configuration showed the lowest production cost for bioethanol, followed by
SSCF-C_RECY, C_RECY-C_RECY and C_RECY-C. As far as xylitol production is

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© 2013 Academia Mexicana de Investigación y Docencia en Ingeniería Química (AMIDIQ)
ISBN: 978-607-95593-1-1
 Memorias del XXXIV Encuentro Nacional y III Congreso Internacional de la AMIDIQ
7 al 10 de mayo de 2013, Mazatlán, Sinaloa, México

concerned, the production costs have the same order, with the difference that the same cost
for xylitol production was found for C_RECY-C and C_RECY- C_RECY.

Table 2. Bioethanol and xylitol production cost and potential profit for producing xylitol
% of difference % of difference % of
Production Production
on bioethanol on potential difference on
cost for cost for
Process profit with profit with total profit
bioethanol, xylitol,
configuration respect to respect to with respect to
USD/gal- USD/gal-
SSCF SSCF SSCF
ethanol xylitol
configuration configuration configuration
C_RECY-C 2.42 0.0078 -90.4% 20.9% -44.4%
C_RECY-C_RECY 2.15 0.0078 -49.8% 20.3% -20.8%
SSCF-C 1.53 0.0054 0.0% 0.0% 0.0%
SSCF-C_RECY 1.71 0.0077 29.9% 18.4% 25.1%

Taking into consideration the SSCF-C configuration as reference, since has the lowest
production cost for bioethanol and xylitol production: A comparison of the C_RECY-C and
SSCF-C, even though the potential profit was around 20.9% higher for the C_RECY-C, the
ethanol production cost was 58.2% higher than the obtained in the SSCF-C process
configuration, which can be really significant at industrial scale, for instance, when total
income was compared, it was seen that the profit was 90% less in the C_RECY-C than in
the SSCF-C. Regarding to C_RECY- C_RECY compared with SSCF-C, the results were
quite similar for potential profit with respect to the reference process configuration, but for
the bioethanol production cost this was 1.4 times higher than SSCF-C and the bioethanol
profit was lower by 49.8%. As far as SSCF-C and SSCF-C_RECY differences were
concerned, the potential income for SSCF-C_RECY was 1.18 higher than the reference
process configuration and the variation for bioethanol production cost was found to be
11.8% more expensive for SSCF-C_RECY, but the incomes for the produced ethanol was
29.9% higher for the SSCF-C_RECY.
As a first screening relying on the production cost, the SSCF-C seemed to be the best
process configuration, but whether the incomes from bioethanol and xylitol productions
were taken into account, the best process configuration was the SSCF-C_RECY. Moreover,
the total profit for the total process was 25.1% superior for the SSCF-C_RECY. Therefore,
it was important to make a complete process analysis for the economics for the best
selection of the process configuration.
One of the main reasons about the difference on the bioethanol profit between SSCF-
C_RECY and SSCF-C was the total produced ethanol; for instance, a previous study [7]
showed that the ethanol/dry-biomass ratio was 0.18 and 0.12 for SSCF-C_RECY and
SSCF-C, respectively. Therefore, the profit obtained for SSCF-C_RECY was reasonability
understandable since the production was 1.5 times with respect to SSCF-C. Regarding to
xylitol production, the central difference was due to the flowrate in the streams leaving
from the distillation columns; that is, for the SSCF-C_RECY configuration, the amount of
xylose and glucose available in the stream entering to the reactor to be converted into
xylitol was higher when compared with SSCF-C.

Concluding remarks
This study has presented the addition of a xylitol production section to the previous
extended version of the DLB 1.0 modeling platform aiming to start with the development

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© 2013 Academia Mexicana de Investigación y Docencia en Ingeniería Química (AMIDIQ)
ISBN: 978-607-95593-1-1
 Memorias del XXXIV Encuentro Nacional y III Congreso Internacional de la AMIDIQ
7 al 10 de mayo de 2013, Mazatlán, Sinaloa, México

of a biorefinery modeling platform. The introduction of the xylose conversion section

allowed analyzing the process flowsheet from the bioethanol and xylitol production point of
view, permitting to make a more detailed analysis in terms of the likely profit; where the
best process configuration when combining both products was the SSCF-C_RECY having
25.1% more incomes compared to the SSCF-C. For future work, it is planned to have the
same extension in the DLB 1.0 modeling platform for the remaining process configurations
presented by Morales-Rodriguez et al. [7], as well as the addition of the unit operations for
the production of xylitol and other high value-added products under the biorefinery
concept, thereby, providing a global vision of the scope of biomass processing. Hence, this
extended and new modeling platform would allow having a clear picture about the
reliability about a certain particular production route through the use of a mathematical
modeling approach.
Acknowledgments
The authors acknowledge Dr. Sarote Sirisansaneeyakul for facilitating the code of the
mathematical model for a batch reactor to produce xylitol from xylose.
References
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