chemical engineering research and design 1 0 7 ( 2 0 1 6 ) 91101

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Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Technical and economical evaluation of bioethanol

production from lignocellulosic residues in Mexico:
Case of sugarcane and blue agave bagasses

Iliana Barrera a , Myriam A. Amezcua-Allieri b , Lorena Estupinan b ,

Tabata Martnez b , Jorge Aburto b,
a Centro de Investigacin en Biotecnologa, Universidad Autnoma del Estado de Morelos, Av. Universidad 1001,
CP 62209 Cuernavaca, MOR, Mexico
b Biomass Conversion Department, Instituto Mexicano del Petrleo, Eje Central Lzaro Crdenas Norte 152,

Col. San Bartolo Atepehuacan, CP 07730 Mexico City, DF, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: Bioethanol is the main biofuel used in Brazil and USA, produced from sugarcane and corn.
Received 19 June 2015 Nevertheless, the use of food to produce ethanol has to be replaced by agroindustrial waste or
Received in revised form 20 energy crops. The alternative raw material for bioethanol production in Mexico could be sug-
September 2015 arcane and blue agave bagasses. In this work, we built a complete simulation process using
Accepted 9 October 2015 Superpro Designer software considering only the upstream units of fermentation for the
Available online 24 October 2015 technical and economical evaluation of lignocellulosic ethanol. Such consideration is based
on a state-of-the-art analysis of the technology, indicating that technical and economical
Keywords: bottlenecks include pretreatment, saccharication and hexoses and pentoses fermentation.
Process simulation The simulation was carried out at different efciency levels through a statistical analysis
Bioethanol of surface responses and, three different saccharication processes to analyze ethanol pro-
Lignocellulosic residues duction in terms of complete substitution of oxygenates in gasoline distributed in Mexico.
Sugarcane The results indicate that ethanol production cost is 1.34 and 1.46 USD/gallon and poten-
Blue agave tial production is 40.13 and 1380 MM gallon/year using blue agave bagasse and sugar cane
bagasse, respectively.
2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction to an effort to reduce vehicles emissions that contribute to

Biofuels are obtained from biomass through chemical, physi-
cal or biological processes. The main biofuels currently in use
around the world are biodiesel, biogas, and bioethanol; such
biofuels are used neat or more often mixed with fossil fuels
for vehicles and less for electricity generation (wood pellets
and biogas). Biofuels are produced from raw materials coming
from agriculture, forestry and cattle industries but also from
organic wastes and residues from all kind of industries. The
interest on biofuels in Mexico is very recent and mainly due
the formation of ground-level ozone and greenhouse gases,
but also to impulse and diversify its agriculture practices and
industrial activities. Also, the blending of biofuels with fossil
fuels may help to diminish the decay of crude oil reserves.
In 2008, the Mexican Congress approved the Bioenergetics
Act that favors the use of biodiesel and bioethanol in diesel
and gasoline sell in Mexico by Petrleos Mexicanos (PEMEX),
the State-owned company that explores, produces, renes,
and transforms crude oil. Concerning to gasoline oxygenates,
PEMEX produces some Methyl tert-butyl ether (MTBE), Ethyl

Corresponding author. Tel.: +52 5591758247; fax: +52 5591758429.
E-mail address: jaburto@imp.mx (J. Aburto).
http://dx.doi.org/10.1016/j.cherd.2015.10.015
0263-8762/ 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
92 chemical engineering research and design 1 0 7 ( 2 0 1 6 ) 91101
tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME), but
the rest is imported due to rening and conversion limitations
in current PEMEXs facilities. One alternative to current oxy-
genates is bioethanol, that can be used neat, but usually mixed
with gasoline at different ratios and commonly called gaso-
hol. Brazil and USA are the main producers of ethanol around
the world with a production over 73,406 million of liters per
year from sugar and maize, respectively (Renewable Fuels
Association (RFA), 2013). Moreover, the Renewable Fuel Stan-
dard (RFS) ensures that the cellulosic biofuels volume standard
is tied directly to production, which acknowledges the efforts
of advanced biofuel investors and innovators (Coleman, 2013).
In Mexico, ethanol production comes primarily from sugar
cane fermentation and produced about 15.3 million of liters in
20112012 (Comit Nacional para el Desarrollo Sustentable de
la Cana de Azcar, 2015a); but it is used only on conventional
industries as spirits, pharma, chemical and cosmetics. On
the other side, Mexico is sufcient in sugar production, in
20132014 exported 2.5 millions of tons (Comit Nacional para
el Desarrollo Sustentable de la Cana de Azcar, 2015b) that
could be instead transforming to ethanol. Nevertheless, the
production of ethanol is insufcient to satisfy the potential
demand for bioethanol and PEMEX could be attracted to
import ethanol from producing countries as USA and Brazil.
Such policy may have a negative important impact on the
agriculture, industrial, economic and social development in
Mexico.
Nowadays, there are many technical and economical
limitations for production of ethanol from lignocellulosic
materials and a lot of research is currently done to develop
a suitable technology. Here, process simulations may be a
helpful tool to identify and understand technical bottle-
necks that impact the full economy process. Indeed, some
process simulation-based works have been carried out to
understand the effect of a double acid hydrolysis of a theo-
retical lignocellulosic material on ethanol production (Zhang
et al., 2009), to estimate the cost of corn dry-grind pro-
cess for ethanol production (Kwiatkowski et al., 2006), an
analysis for feasibility studies of bioreneries (Sadhukhan
et al., 2008); and several works on optimization and cost
estimation of a wheat biorening (Arifeen et al., 2007a,b,
2009; Du et al., 2009; Misailidis et al., 2009). In Mexico, some
important but scarce works have been done on engineered
microorganisms for ethanol production, (Romero et al., 2007;
Martinez et al., 2000; Chuck-Hernandez et al., 2011; Orencio-
Trejo et al., 2010) kinetics of hydrolysis of sugarcane bagasse
(Aguilar et al., 2002; Conde-Meja et al., 2012; Pavon-Orozco
et al., 2012); and comparative hydrolysis and fermentation
of sugarcane and agave bagasses (Hernndez-Salas et al.,
2009). Nevertheless, there is no information, to our knowl-
edge, concerning the process simulation of sugarcane and
Blue agave bagasses for ethanol production in Mexico. This
work presents results of the technical and economical evalua-
tion of production of bioethanol from lignocellulosic residues
largely found in Mexico, sugarcane and Blue agave bagasse,
co-products of sugar reneries and Tequila industries. We
built the process simulation using currently values for eco-
nomics and varied the technical efciencies of fermentation
up-stream processing units in order to ascertain the tech-
nical limitations and their impact on the economics of the
process. Finally, we analyze the prospect about the possi-
ble impact of lignocellulosic bioethanol in demand scenarios
for its introduction in the gasoline produced by PEMEX in
Mexico.
Table 1 Dry-basis composition of sugar cane (49%
dry-basis; Unin Nacional de Caneros, 2007) and agave
(51% dry-basis; Iniguez-Covarrubias et al., 2001)
bagasses used in simulations.
Component Base-case blue Base-case sugar
agave bagasse (%) cane bagasse (%)
Cellulose 43 42
Hemicellulose 19 28
Lignin 15 20
Other polysaccharides 13 4.6
Saccharose 10 3
Ash ND 2.4
2. Materials and methods
2.1. Process description
2.1.1. Feedstock and composition
Blue agave (Agave tequilana Weber var.) is cultivated in vast
zones of west-central and northeastern Mexico in 138,236 ha
and harvested (Jima in Spanish) for Tequila manufacture
(Sistema de Informacin Agroalimentaria y Pesquera (SIASP),
2009). The blue agave pinecones (pina) without leaves are
cooked to hydrolyze inulin to fermentable monosaccharides.
After cooking, the pinecones are grinded and pressed to
extract the maximum syrup and maximize yield. Then, the
residue obtained from the process is the agave bagasse
(352,200 metric tons per year), which may be burned to gener-
ate heat and steam at the distillery but is frequently used as
fertilizer on elds.
On the other side, sugarcane (Saccharum ofcinarum)
is cultivated in almost all Mexico (774,243 ha; Sistema de
Informacin Agroalimentaria y Pesquera (SIASP), 2013) and 53
sugar reneries produce diverse sugar grades and molasses.
Some of them produced around 19.3 million liters of ethanol
in 2009 according to the sugarcane union (Unin Nacional
de Caneros). The residue obtained from the process, sugar
cane bagasse (14,870,846 metric tons/year), is mostly used
to generate heat and steam for the sugar renery and only
3% was processed sometime for paper production (Gonzalez-
Cesar, 2002). One advantage to produce ethanol from blue
agave and sugarcane bagasses is that these residues are
concentrated in Tequila industries and sugarcane reneries,
where they may be transformed to ethanol without extra
cost for transportation. In the case of blue agave bagasse,
it contains less hemicellulose and lignin that sugar cane
bagasse (Table 1) which makes it attractive as a source of
fermenting sugars produced by conventional chemical and/or
biologically hydrolysis and saccharication.
2.1.2. Process steps
The process model was built on software for process simula-
tions (SuperPro Designer ) and describes ethanol production
from grinded bagasses to ethanol dehydration (Fig. 1). Fuel
ethanol production from raw materials includes three major
steps (pretreatment, saccharication and fermentation) that
are the main units studied in the present work since they
are still on development; represent the bottleneck of the
process and main sources of ethanol production cost. The
fermentation downstream process units (ethanol distilla-
tion/drying and solid treatment) were built on the basis of
a corn-grind process for ethanol production (Linerio-Gil and
Guzmn-Carrillo, 2004) since we considered that technologies
concerning ethanol purication and solid treatment (lignin
 chemical engineering research and design 1 0 7 ( 2 0 1 6 ) 91101 93

Fig. 1 Biorenery process model of ethanol production from for sugarcane and agave bagasses.

and other solids) are mature and only small advances need
to be done.
2.1.3. Biomass pretreatment
Its purpose is to increase the accessibility of biomass through
the formation of pores and fractures, the removal of lignin,
the partial or total hydrolysis and solubilization of hemicel-
lulose and the partial hydrolysis and loss of the crystalline
structure of cellulose. Such pretreatment should then favor a
posteriori conversion of polysaccharides into fermentable sug-
ars with the minimal presence of fermentation inhibitors as
furfural derivatives. Many pretreatments are in literature and
grouped as physical, chemical, physicochemical and biological
processes (Taherzadeh and Karimi, 2008).
Chemical pretreatments consider the most promising for
cellulose exposition to saccharication agents (Sousa-Costa
et al., 2009). Among the chemical oxidants, ozone is highly
reactive toward compounds with functional groups with high
electron densities, such as those present in lignin (Garca-
Cubero et al., 2009). There are some reports on the literature
of the utilization of ozone to remove lignin of lignocellu-
losic materials, for example newsprint and magazine (Kojima
and Yoon, 2008), poplar sawdust (Vidal and Molinier, 1988),
cotton straw (Shefet and Ben-Ghedalia, 1982), cereal straw
(Garca-Cubero et al., 2009), sugarcane bagasse (Travaini et al.,
2013), Bermuda grass (Lee et al., 2010). The ozonolysis pro-
cess does not generate toxic degradation products (furfural
and hidroxymethylfurfural) that interfere with subsequent
enzymatic hydrolysis and fermentation. Further, ozone reac-
tions are performed at ambient temperature and pressure (Lee
et al., 2010). By these technical advantages, we chose ozonoly-
sis as pretreatment. Since the cost of ozone generation is one

Table 2 Base reactions considered in process simulation of bioethanol production from sugar cane and agave bagasses.
* Mass stoichiometry; ** Mol stoichiometry; [Cellulose]
amorphous : amorphous cellulose; [Hemicell]sol : soluble hemicellulose;
[Lignin]ox : oxidized lignin; PS: Other polysaccharides; S: saccharose; NFM: non-fermentable monosaccharides.
Pretreatment by ozonolysis
*
Sugar cane bagasse +0.03 Ozone 0.42 [Cellulose]amorphous + 0.28 [Hemicell]sol +0.20 [Lignin]ox +0.03 O2
*
Agave bagasse +0.03 Ozone 0.43 [Cellulose]amorphous + 0.19 [Hemicell]sol +0.15 [Lignin]ox + 0.03 O2
Saccharication by enzymes
*
0.9 Cellulose +0.1 H2 O Glucose
*
0.9 [Hemicell]sol +0.1 H2 O 0.1 Glucose+ 0.9 Xylose
*
0.9 PS +0.1 H2 O NFM
**
Saccharose +H2 O Glucose+ Fructose
Hexose fermentation
**
Glucose 1.9 Ethanol +1.9 CO2 + 0.05 Biomass
**
Fructose 1.9 Ethanol +1.9 CO2 + 0.05 Biomass
Pentose fermentation
**
3 Xylose 4.9 Ethanol +4.9 CO2 + 0.05 Biomass
94 chemical engineering research and design 1 0 7 ( 2 0 1 6 ) 91101
disadvantage of this pretreatment, we consider useful to build
a model that helps to analyze the scenario in which the pro-
cess turns out to be protable. The reactions simulated on
SuperPro Designer in the pretreatment by ozonolysis and
operational conditions are shown in Tables 2 and 3, respec-
tively.
2.1.4. Saccharication
The polysaccharides present in biomass must be hydrolyzed
into fermentable sugars (hexoses and pentoses) with min-
imum sugar degradation through thermal, chemical or
enzymatic hydrolysis. This hydrolysis is rather difcult
because of the characteristics of the -1,4-glucosidic bond that
confers the formation of a high crystalline structure in cel-
lulose and by the presence and content of lignin, the glue
between cellulose and hemicellulose, which limits the accessi-
bility to saccharication agents. This process step is critical to
obtain acceptable sugar content in syrups that will depend on
the specicity, efciency and cost of saccharication agents.
Details about chemical properties of biomass holocellulose,
hemicelluloses and -cellulose may offer a good opportunity
for designing more efcient enzyme cocktails for substrate
saccharication (Szczerbowski et al., 2014). However, we simu-
late here the use of a complex cocktail of enzymes that allows
the hydrolysis of cellulose and hemicellulose to fermentable
sugars, mainly glucose and xylose. Sucrose is hydrolyzed to
glucose and fructose while other polysaccharides (PS) produce
non-fermentable monosacharides (NFM, see Table 2). Opera-
tional conditions for simulation of saccharication are shown
in Table 3. Here, saccharication and fermentation are sepa-
rated processing units.
2.1.5. Fermentation
Fermentation process from any material to contain sugar
could produce ethanol. Raw materials used in the manufac-
ture of ethanol can be classied into: sugar (sugarcane, sugar
beets, molasses and fruits), cellulose (wood, agricultural and
domestic residues and paper mills) and starch (corn, cassava,
potatoes and roots crops).
These fermentable compounds are transformed to ethanol
and CO2 by microorganisms. Several microorganisms are used
for ethanol production such as bacteria, yeasts and fungi. The
most used microbe are the yeasts, and Saccharomyces cerevisiae
is preferred. S cerevisiae can produce ethanol at concentra-
tion up to 18% v/v (Cot et al., 2007). This yeast is recognized
as safe (GRAS), it can ferment simple sugar as glucose, man-
nose, galactose and fructose and disaccharide as sucrose and
Table 3 Experimental conditions in simulation
processing of sugar cane and agave bagasses to
bioethanol.
Process Conditions
Pretreatment by 25 C; residence time 1 h; 0.03 kg
ozonolysis O3 /kg bagasse; 38% solids
Sacharication 50 C; residence time 5 h;
0.011 kgenzymes /kgbagasse ; 38% solids
Fermentation of 28 C; residence time 72 h;
hexoses and pentoses inoculum of 1% yeast fermenting
glucose, fructose and xylose; up to
25% fermentative sugars in syrup.
Annual operating time Sugar cane bagasse: 3960 h due to
only one harvest season (Zafra)
Agave bagasse: 7920 h due to
year-round harvest season (Jima)
maltose. S. cerevisiae (wild type) cannot fermented C5 sugars,
as xylose present on the syrups from lignocellulosic mate-
rials. Therefore, xylose fermentation is a challenge because
only a few traditional ethanol-producing microorganism uti-
lize xylose as a carbon source. The use of glucose and xylose
to produce ethanol is essential for economic to achieve a
protable conversion of lignocellulosic biomass to ethanol
as was reported by Bansal et al. (2013), Sassner et al. (2008)
and Kumar and Murthy (2011). Therefore it is important the
efforts to generate microorganisms capable to use xylose as
a carbon source to produce ethanol, as reported by Jeffries
and Shi (1999), Ingram et al. (1987), Zhang et al. (1995), Lynd
et al. (2002), McMillan et al. (1999), Sun and Cheng (2002),
etc. Current research focuses on the development of inhibitor
resistant (furfural, hidroxymethylfurfural and organic acids),
osmophile, thermophile (capable to growth at 4050 C), and
versatile microorganisms able to ferment hexoses and pen-
toses.
In this critical step, we assumed that fermentation is
carried out by an adequate and capable microorganism or
complex inoculum that ferments hexoses and pentoses to
ethanol and carbon dioxide (Table 2) and the fermentation was
carried out on a batch process. Simulated reactions and opera-
tional conditions of fermentation are shown in Tables 2 and 3,
respectively.
2.1.6. Down-stream process
Next step of the production of ethanol is downstream process.
Nowadays, there is a lot of information about the different
strategies to separate, puried and concentrated ethanol from
microbial fermentation. The technology involved is mature
enough; through this the downstream step was based on
a corn-grind process for ethanol production. Downstream
processing consisted of ethanol recovery using distillation and
molecular sieves, co-product recovery and wastewater treat-
ment.
The beer obtained from fermentation is sent to a degasser
drum to ash off the vapor consisting primarily of ethanol,
water and carbon dioxide. Any uncondensed vapor together
with carbon dioxide is sent to the scrubber prior venting
or recovery. Vapors are condensed and mixed with liquid
stream prior to distillation and dehydration through the con-
current action of beer column, rectier, stripper and molecular
sieves. The distillate obtained after molecular sieve treatment
is about 99.6% pure ethanol. The outlet of the beer column
contains water and non-fermentable materials such as lignin,
protein, oil, bers, etc. that are sent to solid treatment. Such
dried solids could be used or sold for burning, cattle feed or
chemical specialties.
2.1.7. Cost model description
Computer simulations to model and predict the costs of pro-
duction have been used with success for many industrial
processes. They provide the ability to estimate the effect
of increasing costs of raw materials or utilities, and the
incorporation of new technologies. Starting with a base-case
scenario and designing the model effectively allows the user to
estimate results of alternative processes with condence. Pre-
viously models of ethanol production process (McAloon et al.,
2000) were developed using a combination of Aspen Plus
(Aspen Technologies Inc., Cambridge, MA), and Microsoft
Excel (Microsoft Corporation, Redmond, WA) and SuperPro
Designer .
 chemical engineering research and design 1 0 7 ( 2 0 1 6 ) 91101
Table 4 Raw material and chemical costs for bioethanol production.
Raw material Cost ($/kg)
Sugar cane bagasse 0.016
Agave bagasse 0.039
Pretreatment agent 1.68
Hydrolytic enzymes 3.5
Inoculum 2.3
Steam electricity (/kW h) 0.042 5
SuperPro Designer Version 5.5 (Intelligent Inc., Scotch
Plains, NJ) allows calculation of the economics, considering
prices of several chemicals used in the production, in order
to evaluate modications and efciencies of the ethanol pro-
duction process. Since sugar cane production in Mexico is
seasonal (5 to 6 months), we assumed that the annual operat-
ing time to process sugarcane bagasse is 3960 h. On the other
side, blue agave is harvested all year round due to diverse
maturities of agave plants and needs of the tequila factories
with an annual operating time of 7920 h. We assume then a
plant capacity of 100 and 200 thousand metric tons/year for
sugarcane and blue agave bagasses, respectively. The informa-
tion in the model is representative of a modern facility and is
not specic of a particular plant. The economics of the process
were calculated assuming prices in Mexico of lignocellulosic
bagasses inoculum price is 2.3 USD/kg (Kumar and Murthy,
2011). The hydrolytic enzymes price was set to 3.5 USD/kg
according to Novozyme, while ozone price was set at a price
of 1.77 USD per kilogram (Table 4). The selling price of solid
coproduct was set to $0.005 USD/kg. Capital costs for man-
ufacturing plants were not considered as part of the study
since scale economy must be considered in order to furnish
the ethanol demand in Mexico.
2.2. Experimental design for ethanol production
In order to observed the effect of different efciencies of
upstream processing units on ethanol production and cost,
we built an experimental design conformed by four units as
experimental factors (ozonolysis, saccharication, fermenta-
tion of hexoses and pentoses) at three levels (20, 60 and 100% of
unit efciency; coded factor X = 1, 0, +1, respectively). These
levels represent the theoretical efciency of conversion for
every unit, i.e. the rst unit efciency set at 20%; the sec-
ond unit, efciency set at 100%, would convert the 100% of
such initial 20% and so on. The experimental responses are
yield (gallons EtOH/metric ton biomass) and production cost
(USD/gallon) of ethanol. The response surfaces were estimated
using a Factorial design 43 with 18 experimental runs. For
every experimental run, the level values were feed to the sim-
ulator and the energy and matter balance as well as economics
was calculated. Statistical analysis was carried out using the
software Statistica v. 6.
2.3. Sensitivity analysis
Here, we carried out a sensitivity analysis of the effect of ligno-
cellulosic bagasse and enzyme prices on ethanol production
95
Description
Pith and depithed bagasse obtained from sugar cane
processing (Unin Nacional de Caneros, 2007)
Pith bagasse obtained from Tequila production (Comisin
Tequilera, 2013)
Ozone used in the oxidation of lignin which renders
accesible cellulose and hemicelullose to enzymatic attack
(Lee et al., 2010)
Mixture of cellulases, hemicellulases and cellobiases
capable to hydrolize cellulose and hemicellulose to glucose,
fructose, xylose (Novozyme)
Microorganism capable to transform glucose, fructose and
xylose to bioethanol (Kumar and Murthy, 2011)
Utilities used for plant operation.
cost. For that, we xed the overall process at 100% efciencies
for all studied processing units.
2.3.1. Description of scenarios for ethanol production and
potential demand: Base cases A, B and C
We propose three scenarios of technical feasibility with the
intention to analyze the impact of efciency pretreatment,
saccharication and fermentation of pentoses and hexoses
on the ethanol cost production and yield. Case A: efciency
of pretreatment and saccharication set at 60%; efciency
of fermentation of hexoses and pentose set at 90%. Case B:
efciency of pretreatment and saccharication set at 90%; ef-
ciency of fermentation of hexoses and pentose set at 90%. Case
C: efciency of pretreatment and saccharication set at 90%;
efciency of fermentation of hexoses and pentose set at 90
and 0%, respectively.
3. Results and discussion
3.1. Simulation
Composition of lignocellulosic bagasses differed in hemi-
cellulose, lignin and sucrose content (Table 1). Blue agave
bagasse contains less of hemicellulose and lignin that may
affect ozonolysis, saccharication and fermentation efcien-
cies. Indeed, the lower content of lignin should be made more
accessible polysaccharide structures to hydrolysis attack on
the saccharication step. With blue agave bagasse, the saccha-
rication process and the use of conventional strains for single
fermentation of hexoses could be more efcient than in sug-
arcane bagasse with a higher content of pentoses and lignin.
Moreover, higher content of sucrose in blue agave bagasse
makes it a valuable raw material for ethanol conventional fer-
mentation. Nevertheless, the cultivated area of blue agave and
potential bagasse production in tequila factories is 5.6 times
and one order of magnitude smaller than sugarcane area and
bagasse production, respectively.
We built an ethanol plant to process 100 and 200 thousand
metric tons with an annual operating time of 3960 and 7920 h
as reported above of sugarcane and blue agave bagasses,
respectively. Since the fermentation process were considered
technical and scientically limited today, the efciencies of
the process steps were varied to evaluate the economic impact
on the price of ethanol. Biomass pretreatment is ozone-
based, a well-known oxidizer, that may depolymerize lignin to
oligophenols and other smaller molecules as syringaldehyde
and p-hydroxibenzaldehyde (Quesada et al., 1998). Biomass
saccharication was undertaken by a hypothetic enzyme
96 chemical engineering research and design 1 0 7 ( 2 0 1 6 ) 91101

Fig. 2 Surfaces response for ethanol production cost from blue agave (up) and sugar cane (down) bagasses. Efciencies of
fermentation of hexoses and pentoses set at 95%.

cocktail able to hydrolyze all polysaccharides present in
bagasses. In the fermentation process, the simulation was
based on a microorganism capable to ferment both, hexoses
and pentoses. The simulations were carried out to know the
effect of efciencies of the three studied processing units on
the ethanol production cost and yield. The 18 simulations
carried out in Superpro Designer were adjusted to response
surfaces for yield and production cost of anhydrous ethanol
using Statistica v. 6 (Figs. 2 and 3). The efciencies of the pre-
treatment, saccharication and fermentation of hexoses and
pentoses were varied from 20, 60 and 100%, (coded value from
1, 0 and +1) in simulations for these response curves.
With regard to ethanol production cost, we observed that
this response diminished to values close to 1 USD per gallon
of ethanol with increasing efciencies of both pretreatment
and saccharication processes for both bagasses (Fig. 2). This
comes from the higher production of ethanol that low pro-
duction costs since the plant scale was maintained all over
the simulations. Pretreatment and saccharication efciency
on ethanol production costs, have a smaller impact on blue
 chemical engineering research and design 1 0 7 ( 2 0 1 6 ) 91101 97

Fig. 3 Surfaces response for ethanol production yield from blue agave (up) and sugar cane (down) bagasses. Efciencies of
fermentation of hexoses and pentoses set at 95%.

agave bagasse than on sugarcane bagasse. Here, we must
keep in mind that a higher efciency in the pretreatment of
agave bagasse means that more lignin and hemicelluloses are
removed with the same feed of ozone since its less content.
In the saccharication step, the production cost of ethanol
from blue agave slightly varied with higher efciencies. Since
the dose of the enzymatic cocktail was maintained constant
in all simulations for both bagasses (0.011 kgenzymes /kgbagasse ,
Table 3), the small variation in blue agave case should come
from lower polysaccharide content (62%) than in sugar cane
bagasse (70%).
Moreover, response curves for ethanol yield were similar
in shape for both blue agave and sugarcane bagasses, but
the latter allowed higher yields (Fig. 3). This higher response
should come from the higher polysaccharide content of sug-
arcane bagasse. The theoretical ethanol yield for blue agave
and sugarcane bagasse, as calculated by the ethanol calcula-
tor from Department of Energy (DOE), correspond to 107.9 and
122.1 gallons per metric ton (Quesada et al., 1998), respectively.
Here, the ethanol production comes primarily from the hexose
component since both biomasses contain around 4243% of
cellulose (Table 1) with a calculated yield around 7274 ethanol
98 chemical engineering research and design 1 0 7 ( 2 0 1 6 ) 91101
Fig. 4 Sensitivity analysis of production cost of ethanol to
the price of blue agave and sugar cane bagasses.
gallons per metric ton. In the simulation, the efcient and
exclusive enzymatic hydrolysis of cellulose produces glucose
that can be easily transformed to ethanol through conven-
tional yeast. When the fermentation of hexoses was set at 90%
efciency (case C), we obtained 90.6 and 68.6 gallon per met-
ric ton of ethanol for blue agave and sugarcane bagasses. With
respect to ethanol production cost at these conditions, the val-
ues were 1.68 and 2.19 USD per gallon, respectively. Additional
fermentation of pentoses at 90% resulted in 113.52 and 102.39
gallons per metric ton; and the ethanol cost in 1.34 and 1.46
USD/gallon for blue agave and sugar cane bagasses, respec-
tively. It is clear that a more economical production from both
bagasses requires the additional hydrolysis of hemicellulose
and fermentation of pentoses present in biomass. Sassner
et al. (2008) found the same conclusion on their model for
three different lignocellulosic material (Salix, corn Stover and
spruce).
3.2. Sensitivity analysis
The biomass price may largely vary due to regional and inter-
national factors as well as its valorization as a commodity
instead of a residue. The cost of the raw material represents
one of the most important variable as it represents about 35%
on total production cost (Piccolo and Bezzo, 2009; Bansal et al.,
2013; Sassner et al., 2008). Then, the price of the biomass will
determine current and future investments on ethanol plants
as well as economic and nancial feasibility.
Models were built with different bagasse prices to esti-
mate the sensitivity of the production cost of ethanol (Fig. 4).
We considered the target cost of ethanol between 1.07 and
1.23 USD per gallon according with the National Biobased
Products and Bioenergy Coordination Ofce NBPBCO (2009).
On the other side, PEMEX has considered that ethanol price
should be at least comparable to MTBE price 1.15 USD/gallon;
(Favela, 2006) in order to not affect the selling prices of the two
kinds of gasolines, Magna and Premium, distributed in Mexico.
The cost of the blue agave and sugarcane bagasses from
tequila and sugar industries in 2011 varies around 39 and
16 USD per metric ton, respectively. Ethanol production cost
remained close to the target values of DOE and PEMEX when
bagasse price is lower than 70 USD per metric ton. Therefore,
Fig. 5 Sensitivity analysis of production cost of ethanol to
the price of hydrolytic enzymes.
the Mexican economy shows an interesting opportunity mar-
gin between actual and theoretical maximum bagasse costs.
The sensitivity of the ethanol production cost was also
evaluated against the price of the hydrolytic enzymes (Fig. 5).
This cost is very important since it will also determine the
economic feasibility of lignocellulosic clean hydrolysis to fer-
mentable sugars without production of undesirable furfural
derivatives under mild reaction conditions. The enzyme cost is
lower for sugar cane bagasse since ethanol production is larger
than agave bagasse with the same amount of enzyme. The cost
of ethanol remains below DOEs and PEMEXs target within an
hydrolytic enzyme cost less than 0.6 and 0.5 USD per gallon for
blue agave and sugarcane bagasse, respectively. In the simula-
tions, it was considered the hydrolytic enzyme cocktail has a
very high afnity toward polysaccharide hydrolysis, but it was
used without recycle at a xed enzyme/biomass ratio. It is evi-
dent that enzyme recycle and the use of high active enzymes
(Tu et al., 2007) may further approach the enzyme cost to the
goal of $0.10 per gallon of ethanol.
3.3. Scenarios for ethanol production and potential
demand: Base cases A, B and C
Here, we considered three cases based on the process ef-
ciency of the pretreatment-saccharication and fermentation
of hexoses and pentoses (Table 5). In case A with lower efcien-
cies for both processes, we observed an ethanol production
cost higher than that stated by DOE and slightly smaller than
the requirement of PEMEX-Rening for both bagasses. In base
case B with higher pretreatment-saccharication efciency
(90%), the ethanol production cost fall down the target set by
DOE. The case C considers conventional technology allowing
only the fermentation of hexoses with a slightly increment in
ethanol production costs and a reduction in yield.
In Mexico, the ethanol incorporation to the gasoline pool
might be competitive with the replacement of MTBE and other
oxygenates by PEMEX since no taxes incentives are consid-
ered at all. Then, case A should be considered as an example
of minimum set of process required efciencies satisfying the
Mexican market of ethanol. The MTBE FOB price is around
3.31 USD per gallon (Platts, 2015). Concerning ethanol produc-
tion capacity, PEMEX-Rening has estimated a requirement of
52.8 millions of gallons/year (200,000 m3 /year) of ethanol to
 chemical engineering research and design 1 0 7 ( 2 0 1 6 ) 91101
Table 5 Cost, yield and potential production of ethanol in Mexico from sugarcane and Blue agave bagasses. See text for
case denition.
Sugarcane bagasse
Ethanol production cost (USD/gallon)
Ethanol yield (gallon/metric ton)
Bagasse production (2011, metric ton)
Potential production of ethanol (MM gallons/year)
Blue agave bagasse
Ethanol production cost (USD/gallon)
Ethanol yield (gallon/metric ton)
Bagasse production (2012, metric ton)
Potential production of ethanol (MM gallons/year)
mix with gasoline at 2% of oxygen content. The latter to com-
ply with the demand for the metropolitan Guadalajara area,
the third largest in the country after Monterrey and Mexico
City. Here, we observed that ethanol demand in the Guadala-
jara area may be easily satised from processing of sugarcane
bagasse (ca. 10) but ethanol from blue agave bagasse may
satisfy only the 11.4% demand. Since main production zone
of blue agave is located around Guadalajara area, produced
ethanol might be used for comply with local demand and
the rest should be obtained from other lignocellulosic materi-
als as sugarcane bagasse. The Mexicos ethanol demand was
estimated on 242.5 millions of gallons/year in 2007 (PEMEX,
2009), that might be supply by the Mexican sugarcane indus-
try through the valorization of the bagasse. Indeed, the process
simulation for sugarcane bagasse showed an ethanol surplus
of 2.6, 5.6 and 3.8 times in the cases A, B and C, respec-
tively. Nevertheless, we think that Mexicos ethanol market
should be based on several lignocellulosic residues, regionally-
located, that could satisfy ethanols future demand rather
than favor a single ethanol source as currently done by the
USA and Brazil.
4. Conclusions
We built the process simulations for ethanol production from
sugar cane and blue agave bagasses, two of the main ligno-
cellulosic residues produced in sugar reneries and Tequila
industries in Mexico. Both industries process and concen-
trate in situ a large quantity of bagasses that may be suitable
for further conversion to ethanol. The process simulation
using Superpro Designer allowed the evaluation of tech-
nological, scientic and economical limitations for cellulosic
ethanol technology. Lignin elimination for higher exposure of
cellulose and hemicellulose to hydrolytic systems is needed
in order to maximize the saccharication through high-
efciency enzymes or other catalysts. The obtained syrups
rich in fermentable sugars, both hexoses and pentoses, will
require the use of yeast, bacteria or modied organisms able to
ferment all sugars to ethanol. The analysis of surface response
indicated that the pretreatment of blue agave bagasse has
a minor effect on ethanol cost and yield when compared to
sugar cane bagasse because of less content of lignin and hemi-
cellulose.
The sensitivity analysis showed that the cost of ethanol
could be lower than the DOE and PEMEX target cost, consid-
ering the current price of both bagasses in Mexico and the
hydrolytic enzyme cost up to 0.5 and 0.6 USD/gallon of ethanol
for sugar cane and blue agave bagasses, respectively. In all
studied cases, the ethanol from blue agave bagasse might
be cheaper than from sugarcane bagasse due to the less
99
Case A Case B Case C
5.01 1.46 2.19
48.18 102.39 68.61
13,477,668
649 1380 924.7
2.62 1.34 1.68
57.99 113.52 90.60
352,200
20.4 40.13 31.9
extensive pretreatment and saccharication processes due to
the less lignin content. Ethanol yield is quite similar for both
bagasses because of similar polysaccharide content. Never-
theless, potential production of ethanol from blue agave is far
away to comply oxygenate demand in Mexico. This is due to
the lower production and processing of Agave tequilana weber,
which is three orders of magnitude lower compared to the
sugarcane bagasse. Here, sugarcane bagasse could be a bet-
ter lignocellulosic raw material to produce ethanol since its
major quantity of bagasse and availability around the country.
Nevertheless, we consider that ethanol production in Mexico
should take in consideration other lignocellulosic residues to
develop regional industries of diverse raw materials.
Acknowledgments
Authors thank IMP (Y.60013) and CONACyT for nancial sup-
port through project Y.60013 (151370). I. Barrera acknowledges
her postdoctoral fellowship.
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