Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

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Renewable and Sustainable Energy Reviews

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

Acid pretreatment of lignocellulosic biomass for energy vectors production:

A review focused on operational conditions and techno-economic
assessment for bioethanol production
Juan Camilo Solarte-Toroa, Juan Miguel Romero-Garcíab,c, Juan Carlos Martínez-Patiñob,c,
Encarnación Ruiz-Ramosb,c, Eulogio Castro-Galianob,c, Carlos Ariel Cardona-Alzatea,
⁎

a
Instituto de Biotecnología y Agroindustria, Departamento de Ingeniería Química, Universidad Nacional de Colombia sede Manizales, Km 07 vía al Magdalena, Manizales
Colombia.
b
Department of Chemical, Environmental and Materials Engineering, Universidad de Jaén, Campus Las Lagunillas s/n, 23071 Jaén, Spain
c
Center for Advanced Studies in Energy and Environment (CEAEMA). Universidad de Jaén, Campus Las Lagunillas s/n, 23071 Jaén, Spain

A R T I C LE I N FO A B S T R A C T

Keywords: The acid pretreatment process is the most employed technique used to disrupt the lignocellulosic matrix. Thus,
Acid pretreatment this paper provides an overview of the acid pretreatment considering important aspects related to the operation
Lignocellulosic biomass conditions, yields, future improvements and the potential use to upgrade lignocellulosic biomass in energy
Energy vectors vectors. Moreover, this paper is focused on technical and economic aspects of the use of the acid pretreatment in
Solid acid catalyst
bioethanol production using olive tree biomass as a case study. This review will provide the framework of the
Biochemical conversion
acid pretreatment based on reported applications, experimental and theoretical data. The most well-studied
applications of the acid pretreatment are in bioethanol and biogas production. Furthermore, this pretreatment
has been improved using solid catalysts and by increasing the solids loading. These options have advantages
compared to the traditional way. Even so, improvements in the technical and energy aspects must be performed
to make the implementation of this process viable from an economic and environmental perspective. Instead, the
kinetic modelling and statistical analysis of the acid pretreatment can be postulated as strong tools to predict the
behaviour of different feedstocks under acidic conditions. Moreover, new alternatives to increase the mass and
heat transfer in this process related to reactor design conform a new research field. Regarding the case study, the
acid pretreatment is one of the most energy-consuming stages of bioethanol production. Low solids loadings are
recommended to obtain production costs that are comparable with those reported on the industrial level. In
contrast, a high solids loading allows the environmental impact of the process to be reduced in terms of liquid
waste generation and carbon dioxide emissions. Finally, the acid pretreatment should be included as an effective
method for the biotechnological conversion of lignocellulosic biomass to produce energy vectors once the
technical, economic and environmental drawbacks have been overcome.

1. Introduction reason, the use of renewable energy sources such as wind, sunlight,
hydro-energy and biomass has grown in the last years. Aspects such as
Recent developments and advances in the transport, industrial and the increase of the global energy generation capacity, falling costs, the
building sectors have encouraged the use of renewable resources [1,2]. growth of project investments and advances in enabling technologies
These improvements are related to the operation of cogeneration sys- for power generation have affected positively the development of re-
tems in both the industrial and building sectors, as well as the elec- newable energy [7]. In this way, the progress of renewable heat and
trification of automotive vehicles [3,4]. The initiative to use renewable power production has increased 20.5% and 56.6%, respectively, in the
energy has been promoted to reduce the exploitation and use of non- period from 2007 to 2015. Moreover, in 2017 renewable energy sup-
renewable energy sources such as coal, natural gas and crude oil, which plied about 18.2% of the worldwide energy demand, which has been
have caused a wide variety of environmental issues related to ozone considered as the largest ever growth of this sector [8,9].
depletion, water pollution and solid waste generation [5,6]. For this On the other hand, the progress reached in the biofuels and

⁎
Corresponding author.
E-mail address: ccardonaal@unal.edu.co (C.A. Cardona-Alzate).

https://doi.org/10.1016/j.rser.2019.02.024

1364-0321/ © 2019 Elsevier Ltd. All rights reserved.

Received 8 October 2018; Received in revised form 20 February 2019; Accepted 23 February 2019

Please cite this article as: Juan Camilo Solarte-Toro, et al., Renewable and Sustainable Energy Reviews,
https://doi.org/10.1016/j.rser.2019.02.024
J.C. Solarte-Toro, et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

bioenergy field by industry and academia has caused the partial re- the acid pretreatment as concerns bioethanol production using olive
placement of conventional petroleum-based products by biomass-de- tree biomass as a case study.
rived products [10]. Indeed, biomass supplied about 10.3% (i.e., 59.2
EJ) of the total energy demand in 2017. Moreover, the agricultural 2. Acid pretreatment
sector provided 10% of the total biomass capable of being upgraded
into energy [11]. Nevertheless, the economic feasibility of bio-based The acid pretreatment method has been demonstrated to be highly
products is still an issue that must be evaluated [12]. For this reason, effective at disrupting the lignocellulosic matrix through the cleavage
different countries in Europe, North America and Latin America have of glucosidic bonds, which leads to the transformation of poly-
proposed multiple policy objectives to support the growing renewables saccharides into oligomeric and monomeric sugars [27]. Indeed,
sector. In fact, 87 countries have fixed economic targets for the use of hemicellulose is the main fraction of the lignocellulosic biomass af-
renewable energy, which demonstrates the growing interest in chan- fected by the acid pretreatment technique. Nevertheless, this process
ging the actual oil-based economy into a bio-based economy able to also solubilizes part of the lignin and cellulose, releasing oligomers and
guarantee food and energy security [13,14]. Biomass is one of the most carbohydrates [26]. Even so, acid pretreatment has been researched
used renewable resources to produce bioenergy and high value-added extensively and has been considered the pretreatment technology that
products [15,16]. Special interest has been focused on the use of is closest to being commercialized [28]. Despite the effect of the acid
second-generation biomass (i.e., agroindustrial residues, forest biomass pretreatment on the lignocellulosic matrix, and the increase in the en-
and food waste), attending to the waste-to-energy and circular economy zymatic digestibility of the raw material, different inhibitory com-
concepts, which describe the use of residual biomass to be upgraded pounds produced from the degradation of sugars and decomposition of
and reused [4,17]. Moreover, the use of second-generation biomass lignin, such as aldehydes, ketones phenolic acids, are considered as the
overcomes the discrepancy between food security, the production of main drawbacks of this process [27].
value-added products and the energy vectors obtaining. Therefore, a Previous review articles have shown the advantages and dis-
wide variety of processes such as pretreatment technologies, conversion advantages of different pretreatment technologies in an individual and
alternatives and upgrading routes have been researched to boost the combined way, of lignocellulosic biomass for the production of dif-
potential of this type of biomass [18]. ferent products, such as the case of Alvira et al., In this work, the di-
The pretreatment process is an important stage in the upgrading of luted acid pretreatment is highlighted presenting its advantages respect
second-generation biomass due to the fact that this process breaks down to the other pretreatments able to solubilize hemicelluloses in fer-
the lignin structure, removes hemicellulose, reduces cellulose crystal- mentable sugars. Moreover, Alvira et al., [29] present high yields of
linity and increases the accessible surface area to allow the action of saccharification of the cellulose in the solid fraction after pretreatment.
enzymes and microorganisms [19]. In fact, the purpose of the pre- The production of maximum amount of sugars, pentoses and hexoses,
treatment stage is to efficiently separate and provide easier access to the and the transformation of both into ethanol is fundamental for the
main biomass components [20]. Nevertheless, the full effect of these viability of the process [29]. In this way, some advantages of the acid
advantages is not achieved by a single pretreatment process. For this pretreatment are the use of highly commercial compounds (i.e., in-
reason, different pretreatment methodologies have been researched, organic acids and organic acids), flexibility to be applied at industrial
reported and classified in recent years [21]. The main techniques to level, high hemicellulose solubilization and high glucose yield. Never-
pretreat lignocellulosic biomass are physical (e.g., comminution, hy- theless, some disadvantages of this pretreatment method are related to
drothermolysis, microwave, ultrasound), physicochemical (e.g., steam high cost of acid recovery, high cost of corrosive resistant acid equip-
explosion, ammonia fibre explosion), biological (e.g., fungi, bacteria, ment and the inhibitors formation. Other pretreatments such as liquid
microbes) and chemical (e.g., acid, alkali, solvents, ozone) [20,22]. hot water (LHW), steam explosion and organosolv have been re-
These techniques can be combined to improve the effect on the lig- searched. However, high solvents cost, need for solvent recovery and
nocellulosic matrix as well as to increase the yield and productivity of recycle, partial hemicellulose solubilization, toxic compounds genera-
the desired products, given that the use of a single process can have tion and high-energy consumption are some drawbacks of these pre-
operational problems associated with technical issues such as high en- treatments respect to the acid process [30].
ergy consumption, high reaction volumes and long residence times Solids loading, acid concentration, temperature and residence time
[22]. Despite this, the pretreatment technologies have boosted the use are the main process variables studied in the acid pretreatment process.
of second-generation biomass to produce valued-added products and As responses, the solids recovery, sugars yield, hemicellulose conver-
energy vectors, as well reducing problems related to the use of energy sion, glucose, xylose and furfural concentration have been evaluated for
crops. Among the above-mentioned pretreatment techniques, acid a wide variety of raw materials [24,31–34]. For this, different varia-
pretreatment has been the most widely studied and applied on an in- tions in the acid pretreatment have been made to find the best opera-
dustrial level [23]. tion conditions in terms of technical, economic and environmental as-
The acid pretreatment technology has some advantages compared pects [35–37]. Among these variations can be counted the reactor
to other pretreatment technologies in terms of lignocellulosic matrix configuration (e.g., plug-flow reactor, countercurrent acid extraction,
disruption and amorphous cellulose conversion [24]. Nevertheless, this two-stage processing), the change of the operating conditions (e.g.,
pretreatment technology also has different disadvantages associated pressure increasing, acid concentration decreasing) and the search of an
with the production of inhibitory compounds and wastewater genera- effective method of catalysis (e.g., use of solid catalysts or Lewis acids).
tion with a high acidification potential, aquatic toxicity potential and In this way, the acid pretreatment process can be studied from two
human toxicity potential for both ingestion and exposure [25,26]. In different perspectives. The first takes into account the experimental
this way, an inclusive analysis of the developments achieved by dif- data and yields obtained at different scales. This perspective has been
ferent researchers, the technical benefits and drawbacks of this tech- studied by analysing the effect of the process variables on the above-
nique, as well as the economic and environmental implications must be mentioned responses through the use of statistical approaches (e.g.,
performed to elucidate the importance of the acid pretreatment tech- experimental design). On the other hand, the acid pretreatment process
nology as a fundamental step in the upgrading of second-generation can be studied from a kinetic point of view to predict the behaviour of
biomass. Therefore, this paper provides an overview of acid pretreat- the hemicellulose depolymerization into xylose and inhibitory com-
ment, considering aspects related to the operation conditions, yields pounds. Moreover, this pretreatment technique has also been included
and its role in the production of biomass-derived sugars for obtaining in a wide variety of technical reports to evaluate the economic and
the energy vectors and value-added products. In addition, this paper is environmental feasibility of obtaining biochemical products such as
focused on the technical and economic aspects of the implementation of bioethanol and biogas among others. In accordance with the above, the

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Table 1
Main operating conditions employed to perform an acid pretreatment.
Process Raw material Acid *A.C. (%w/w) *Temp (°C) Time (min) *SL (%w/w) Ref.

Wet pretreatment. Rice straw Sulphuric acid (H2SO4) 0.5 – 1.0 169–190 1–25 10 [55]
Wild rice grass 1.5 121 60 10 [56]
Olive tree biomass 2.0 130 90 20 [57]
Eucalyptus benthamii Phosphoric acid (H3PO4) 0.5–1.0 180–200 5–15 10 [58]
Rapeseed straw 0.3–3.7 145–215 5–60 12 [32]
Sugarcane 0.05–0.2 144–186 8–24 5 [59]
Corn Stover Hydrochloric acid (HCl) 1.0 100–130 20–40 10 [60]
Corn Stover 0.4–1.0 110–130 30–50 10 [41]
Sugarcane bagasse 2–6 100–128 0–300 10 [61]
Macroalgae cellulosic residue (MCR) Solid catalyst (Dowex (TM) Dr-G8) 0–6 110–140 15–60 8–14 [50]
Corn cobs Carbon-based catalyst (C-SO3H) 1.0 140 360 1 [36]
Cellulose Inorganic catalyst (Fe3O4 – SBA – SO3H) 10 150 180 6.6 [62]
Dry pretreatment Corn Stover Sulphuric acid (H2SO4) 2.5–5.0 175 - 190 3–5 [35,52]

*Temp: Temperature, *SL: Solids loading, *A. C.: Acid concentration.

following sections will review the previous aspects. to evaluate the amount of fermentable sugars that can be produced. In
fact, Janga et al.,obtained a sugar yield of 56 g/100 g for aspen wood
2.1. Operating conditions and process variables (i.e., 74% theoretical) and 64 g/100 g for pine wood (i.e., 91%
theoretical) using solutions of sulphuric acid with concentrations of
2.1.1. Wet acid pretreatment 65%, 72.5% and 80% w/w [40]. On the other hand, Miller and Hester
According to the solids loading, the acid pretreatment can be clas- reported a conversion of hemicellulose and cellulose of 73.8% and
sified as wet or dry pretreatment. The wet acid pretreatment is char- 44.4%, respectively, once a two-stage concentrated acid pretreatment
acterized by the use of solids loadings below of 15%w/w [27]. Thus, was applied to pine softwood using a sulphuric acid solution
this way of performing the acid pretreatment of lignocellulosic biomass concentrated at 70% w/w [37]. Finally, Yoon et al. reported that the
involves both mineral acids (e.g., H2SO4, HCl, HNO3, and H3PO4) and concentrated phosphoric acid pretreatment (i.e., 85% w/w) has a
organic acids (e.g., CH2O2, C2H4O2, C3H6O2 and C4H4O4) as catalysts greater effect on bark than woody biomass, obtaining 60% and 40%
[38]. However, different problems associated with the environmental of solubilization of xylan and cellulose, respectively [24]. The
sustainability of the process has caused a need for improvements in this concentrated acid pretreatment process has some disadvantages
pretreatment technique to optimize yields and reduce costs. These related to the high inhibitory compounds generation, the formation of
problems have been solved through the use of solid acid catalysts as salts after a mandatory neutralization step, reactor corrosion by acid,
well as the adjustment of the operating conditions [35,39]. The wet the increased acid catalyst price and industrial safety issues [27].
acid pretreatment process is the most common way used to perform the
hemicellulose disruption of second-generation raw materials. De- 2.1.1.2. Diluted process. The dilute acid pretreatment process is
pending on the acid concentration in the acid solution, this pretreat- considered the pretreatment technology closest to commercialization
ment can be classified as a concentrated or diluted acid pretreatment due to its simplicity, low reagents costs and effectiveness [27]. In the
process. Briefly, the main advantage of concentrated acid pretreatment, same way as the concentrated acid pretreatment, this process is carried
in comparison to dilute acid pretreatment, is the operation at much out using solid to liquid ratios of 1:10. However, the dilute acid
lower temperatures (and longer time), which means lower operation pretreatment only removes the hemicellulosic fraction of the raw
costs. On the contrary, process equipment is usually more expensive materials. Therefore, an enzymatic saccharification process is
because it must be resistant to corrosion. Due to the higher operation required to complete the cellulose hydrolysis [41,42]. In fact, the
temperatures in dilute acid pretreatment, sugar degradation com- dilute acid pretreatment process allows almost complete hydrolysis of
pounds are generally produced. Some of these compounds, e.g., fur- the hemicellulose as well as partial lignin solubilization [43]. Once
fural, 5-hydroxymethylfurfural (HMF), levulinic acid and formic acid, these components have been removed, sugar yields close to 90% can be
etc., have been described as potential inhibitors of the growth of the reached through enzymatic hydrolysis. The operating conditions
fermenting microorganisms used in downstream processing [40]. involve the use of relatively high temperatures (120–215 °C),
pressures (2–10 atm) and low acid concentrations (0% w/w – 5% w/
2.1.1.1. Concentrated process. The main characteristic of the w). In addition, the residence time varies from 10 to 120 min (see
concentrated acid pretreatment is the use of a large amount of acids Table 1), which is lower than the time needed for the concentrated acid
such as sulphuric acid, chloridric acid, phosphoric acid, nitric acid pretreatment method. Indeed, different raw materials have been
among others in high concentrations (i.e., higher than 30% v/v) to pretreated using the dilute acid pretreatment, obtaining an overall
obtain high sugars yields avoiding the saccharification stage using fermentation sugars and solids recovery from 60% to 75% and 35–65%,
enzymes [27]. In this process, both cellulose and hemicellulose are respectively [44–46]. Moreover, the dilute acid pretreatment has been
disrupted into xylose, mannose, arabinose, galactose and glucose. This optimized using the surface response methodology to find the optimum
process can be divided into three stages [27]. The first one is related to temperature, acid concentration and sugars yield [47,48]. In fact, Ruiz
the hemicellulose removal in a pre-hydrolysis step. Then, the cellulose et al. reported a sugars and solids recovery of 65.5% and 40%,
is disrupted to produce cellooligosaccharides. Finally, these are respectively, at an optimum temperature of 167.2 °C and 1.3% w/w
hydrolyzed to produce monomeric sugars. The crystalline structure of of acid concentration, when the dilute acid pretreatment process was
the cellulose is converted into its amorphous form in the first two applied to sunflower stalks [49].
stages, which improves the conversion into value-added products using The dilute acid pretreatment has more advantages from an eco-
microorganisms [20]. The operating conditions of the concentrated acid nomic and environmental perspective than the concentrated acid pre-
pretreatment involve the use of acid solutions with a concentration over treatment due to the low reagents cost, less corrosive effect and amount
30% w/w and room or moderate temperatures (i.e., usually below of acidic waste production [27]. Therefore, this method has been re-
100 °C) [27]. This pretreatment has been employed by several authors searched extensively. Nevertheless, other options such as the use of

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Fig. 1. Acid pretreatment: Review of main process variables, reactor configuration, impact in process sustainability and main industrial products.

solid catalyst have been implemented in recent years. Solid catalysts the dilute acid solution, which helps to improve the mass transfer be-
such as zeolites, ion-exchange resins and carbon-based catalyst are tween the lignocellulosic matrix and the acid catalyst. The residence
being researched. Indeed, Tan and Lee used Dowex (TM) Dr-G8 as time of the presoaking stage is about 12 h at room temperature.
catalyst to pretreat macroalgae cellulosic residue (MCR), obtaining an Nevertheless, this presoaking step is not suitable on an industrial level
optimal catalyst loading of 4% w/w without the formation of inhibitory owing to the large residence times that are needed [52]. Moreover, the
compounds. Moreover, these authors reported that the catalyst could be additional costs related to the system transportation, mixing equipment
used six times without affecting the performance of the process, and storage tanks are included in the economics of the overall up-
reaching glucose yields higher than 95%. The operational conditions grading process. Therefore, He et al. have proposed a way to realize the
were 120 °C and a residence time of 30 min [50]. Similar results were dry pretreatment process without the presoaking stage using co-current
obtained by Qi et al. after pretreating corncobs with a carbon-based feeding of the raw material and dilute sulphuric acid solution [35]. The
acid catalyst (i.e., C-SO3H) [36]. In this study, a xylose yield of 77.5% results obtained by these authors are satisfactory in terms of the sugars
was obtained at 140 °C, 6 h of residence time and catalyst loading of 1% yield, inhibitory compounds formation and xylan removal.
w/w. Both studies concluded that high catalyst loadings affect nega- The operating conditions of the DDAP process involve temperatures
tively the pretreatment process, reducing the sugars yield due to the between 175 °C and 190 °C, residence times from 3 min to 5 min and
presence of sufficient acid sites, which promote undesired side reac- acid concentrations between 2% w/w and 5% w/w (see Table 1). This
tions. In addition, these studies concluded that one of the most im- pretreatment has been applied mainly to corn stover using sulphuric
portant advantages of the use of solid acid catalyst to pretreat lig- acid as catalyst [28,53,54]. Therefore, the DDAP method must be
nocellulosic biomass is its recyclability, which in both studies exceeded evaluated using other lignocellulosic feedstocks and acid solutions to
the fifth use [36,50]. Finally, the environmental impact of the use of extend the knowledge about the feasibility of applying this process on
solid catalyst is lower than the use of homogeneous catalyst due to the an industrial level. He et al. (2013) [28] reported that the DDAP process
easy catalyst recovery in the first case. Therefore, the use of hetero- has a cellulose conversion from 72.1% to 87.1% as well as a furfural
geneous catalyst to perform this type of process could impact the lig- concentration in the pretreated solid between 0.18% and 0.90%, which
nocellulosic biomass upgrading at all levels [6,51]. are lower values compared to the inhibitory compounds formed in the
dilute sulphuric acid process. Finally, Fig. 1 resumes the main aspect
reviewed for the acid pretreatment process.
2.1.2. Dry acid pretreatment
In order to reduce the amount of wastewater produced using the
traditional dilute acid pretreatment, Zhang et al. studied the way to 2.2. Lignocellulosic biomass acid pretreatment: experimental and simulation
reduce the amount of freshwater and steam used by varying two im- approach
portant parameters of the pretreatment process, namely the feedstock-
filling ratio to the pretreatment reactor and the pre-soaking of solids 2.2.1. Experimental yields
ratio [52]. Once these variables were researched, it was possible to The acid pretreatment process, especially the dilute acid method,
propose a pretreatment method in which the amount of dilute acid has been used to evaluate the structural and compositional changes of
solution is minimized. Then, the dry dilute acid pretreatment (DDAP) the raw material in terms of crystallinity index, hemicellulose conver-
operates with a solids fraction that is two times greater than the liquid sion, inhibitory compounds production and sugars obtained. In this sub-
fraction. Therefore, both the feedstock and product are solid materials section, different results reported in the literature are analysed to elu-
without the existence of free water [35]. Theoretically, different acid cidate the overall effect of the acid pretreatment process on different
solutions (e.g., HNO3, H3PO4, and H2SO4) can be used in this pre- lignocellulosic raw materials. Moreover, different definitions to per-
treatment. Nevertheless, few reports related to the use of the DDAP form the assessment of the acid pretreatment are summarized in
process with some of the above-mentioned acids can be found in the Table 2.
open literature, which indicates a research opportunity. The im- The combined severity factor (CSF) is an indicator used to compare
plementation of the DDPA pretreatment has produced similar sugars different dilute acid pretreatments through the combination of three
yields to those reported using the dilute acid pretreatment. The DDAP main variables of the process: temperature, residence or reaction time
process can be performed after a presoaking or impregnation step with and acid concentration [58]. In fact, Castro et al. reported the

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Table 2 yield of 196 g/kg and xylose yield of 111.2 g/kg were reported. More-
Main equations used to evaluate the acid pretreatment and enzymatic sac- over, Hsu et al. reported a total sugars yield of 193 g/kg and xylose
charification performances. yield of 144 g/kg using rice straw as raw material [55]. The CSF used by
Parameter Equation Symbols Ref. these authors was 1.7, which implies as operation conditions 180 ºC,
1 min and 1.0% H2SO4. Finally, Gonzales et al. published the total sugar
Combined severity t: reaction time (minutes) [63] recovery (39–61%) and xylose recovery (73–99%) for empty palm fruit
factor (CSF) TH & TR : Temperature of
CSF=log ⎧texp ⎡ ⎛ H R ⎞reaction
T -T ⎤ ⎫ bunches, rice husk, and pine wood at different CSF (1.6–2.4) [63]. The
⎨ ⎢ ⎝ 14.75 ⎠ ⎦
⎥⎬
-pH and reference
⎩ ⎣ ⎭ °C)
(100 operation conditions were fixed for the temperature and acid con-
Xylose yield Xliq : xylose in liquid [44] centration (i.e., 121 ºC and 5% w/w) and varied for the residence time
phase (g) (30–90 min). In accordance with the above reported results, a similar
X=
Xliq
Xfeedstock : xylose in CSF does not imply similar operating conditions. Nevertheless, similar
Xfeedstock, dry weight
feedstock (g)
results in terms of sugar yield, xylose yield and inhibitory compounds
MW: Molecular weight
MWXylan = 0.88 MWXylose production can be observed. Therefore, this parameter should be used
Glucose yield Gliq : glucose un liquid [60] to evaluate the acid pretreatment of different raw materials to increase
phase (g) the discussion of the obtained results.
G=
Gliq
Gfeedstock, dry weight The acid pretreatment process is also analysed in terms of the solids
Gfeedstock : glucose in recovery. This indicator is used to establish the overall mass balance of
MWGlucan = 0.90 MWGlucose
feedstock (g) the pretreatment stage as well as the total amount of cellulose, hemi-
Inhibitory compounds Iliq : Inhibitor in liquid [64] cellulose and lignin solubilized during the pretreatment. In fact, the
concentration phaseIliq(g)
Inhibitory compounds =Vprehydrolyzate : Volume
solids recovery can vary from 20% to 80% depending on the severity of
Vprehydrolyzate the pretreatment and the type of raw material. For instance, peels de-
(ml)
Crystallinity index I002 : intensity of the 002 [58]
rived from fruit processing are more susceptible to be more than 50%
peak at 2θ solubilized during the acid pretreatment, while solid recoveries higher
CrI= 002 am *100
I -I
I002
Iam : intensity of the than 60% are usually obtained for woody biomass. This difference is
background scatter at 2θ caused by the internal structure of the raw material in terms of cellu-
Saccharification E.H: Enzymatic [47]
lose, hemicellulose, lignin and other compounds (e.g., extractives,
efficiency Hydrolysis.
Se=
g glucose by EH pectin). Ruiz et al. reported a 20% solids recovery after the dilute acid
100 g glucose in pretreated solid
pretreatment using a CSF of 3.26 with a temperature, residence time
Enzymatic hydrolysis N.A. [47]
yield and acid concentration of 200 °C, 30 min and 2% w/v (H2SO4), re-
YEH=
g glucose by EH
spectively [49]. On the other hand, Linares et al. pretreated rapeseed
100 g structural glucose in raw material
Enzymatic digestibility CGlucose : Glucose straw with dilute phosphoric acid, obtaining a solids recovery of 62.7%.
This value was found using a CSF of 2.73 with temperature, residence
CGlucose concentration in liquid
% ED= *100
phase time and acid concentration of 147 °C, 30 min, 2% w/v (H3PO4), re-
1.11GlucanSubstrate SL
GlucanSubstrate : Glucan spectively [32]. These results indicate that the severity of the pre-
content in the pretreated
treatment has a greater effect on the solids recovery indicator. A deeper
raw material (% w/w)
SL: Solids loading. analysis of the effect of the temperature, residence time and acid con-
Solids recovery N.A centration shows that the order from most to least relevant operating
condition in the solids recovery indicator is temperature, acid con-
SR=
Solids after pretreatment
*100
Solids before pretreatment centration and residence time [32]. Thus, an increase in the tempera-
ture solubilizes more solid than an increase in the acid concentration
N.A. Not Apply. and the residence time, reaching differences between 15% and 20% in
the amount of solid recovered. Finally, an overview of the effect of the
optimization of the phosphoric acid pretreatment of Eucalyptus ben- acid pretreatment on different raw materials is presented in Table 3.
thamii, obtaining as the best operation conditions for maximal total
sugars production a temperature of 200 ºC, 5 min and 0.8%, which 2.2.2. Kinetic modelling
corresponds to a CSF of 1.72 [58]. At these conditions, a total sugars Different approaches are used to model the kinetic decomposition of

Table 3
Overview of the effect of the acid pretreatment on different raw materials.
Raw material Type of acid Hemicellulose conversion Xylose yield (g/100 g raw Furfural concentration Solid recovery Crystallinity index Ref.
(%) material) (g/L) (%) (%)

Cassava Sulphuric acid 35.81 4.24 5.00 NR 50.23 [65]

0.01% (w/w)
Rapeseed straw Sulphuric acid 72.00 10.08 0.51 NR N.R. [66]
1.00% (w/w)
Artichoke stalks Nitric acid 89.6 13.20 0.41 66.27 N.R. [67]
5.00% (w/w)
Rice straw Sulphuric acid 84.00 19.40 2.40 31.00 98.40 [43]
0.75% (v/v)
Cotton Gin Waste Sulphuric acid 86.00 13.32 1.83 65.00 N.R. [68]
1.60% (v/v)
Agave lechuguilla Sulphuric acid 70.68 6.38 0.49 45.70 N.R. [47]
1.00% (w/v)
Aspen Wood Sulphuric acid 82.87 9.9 3.3 66.50 N.R. [69]
1.00% (w/v)
Yellow poplar 0.73% (w/w) 70 9.6 N.R N.R N.R [70]

N.R. Not Reported.

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the main polymers that conform the lignocellulosic components. The Table 4
first model used to describe the cellulose decomposition in the presence Parameters of the hemicellulose degradation kinetic degradation for different
of sulphuric acid was proposed by Seaman [71]. Nevertheless, this raw materials.
model has also been applied to the hydrolysis of the hemicellulosic Raw material k1 (1/min) Ea1 ((kJ/ k2 (1/min) Ea2 ((kJ/ Ref.
fraction, which is considered to be mainly composed of xylan. In fact, mol)) mol))
the model considers the polymer decomposition in a first order kinetic
Aspen wood 4.67 × 1016 142.58 6.51 × 1016 155.36 [74]
reaction into monomeric compounds, as well as inhibitory compounds
Balsam 2.19 × 108 76.19 7.59 × 1015 147.56 [74]
formation. Another approach considers that the hemicellulose is com- Basswood 7.73 × 1019 171.20 2.52 × 1013 126.89 [74]
posed of two types of xylan (i.e., fast and slow reacting xylan), and the Red Mapple 3.18 × 1015 133.44 6.83 × 1013 129.64 [74]
same reaction for the inhibitory compounds production as in the case of Switchgrass 4.10 × 1016 141.30 3.73 ×;1017 165.59 [74]
Sugarcane 5.29 × 1013 109.00 N.R. N.R. [75]
the Seaman modelling. This method was published by Esteghlalian
bagasse
et al. [72] Both methods are widely described in the literature and have Poplar 3.30 × 1021 176.70 8.50 × 1010 102.00 [72]
been used to find the kinetic decomposition of the hemicellulosic Corn stover 6.70 × 1016 129.80 3.70 × 1010 98.40 [72]
fraction of different raw materials during the acid pretreatment process. Empty fruit 1.91 × 1024 203.70 1.11 × 1011 110.90 [76]
The reactions considered in both methods are presented below: bunches

Saeman model [73]

Xylan⟶Xylose⟶Furfural
K1 K2
computational fluids dynamics (CFD) to model the conversion of xylan
into xylose and furfural [28].
Esteghlalian et al., model [72]

Fast reacting xylan⟶Xylose⟶Furfural

Kf K2 2.3. Energy vectors production applying acid pretreatment process

Slow reacting xylan⟶Xylose⟶Furfural

Ks K2 The main objective of the acid pretreatment process is to improve
the amount of sugars obtained, which can be used to produce energy
where k1 is the kinetic constant of the xylan degradation, k2 is the ki- vectors (e.g., bioethanol, biogas) and value-added products through
netic constant of the xylose degradation, kf is the kinetic constant of the biotechnological processes. In accordance with the above sections, the
fast xylan decomposition and k s is the kinetic constant of the slow xylan dilute acid pretreatment is widely used to remove only the hemi-
decomposition. The equations allow the mass balances inside an acid cellulosic fraction of the raw material [78,79]. Then, a saccharification
pretreatment reactor to be performed. These are presented for the case stage is performed using an enzymatic complex to produce fermentable
of the Seaman model, or if only the fast reacting xylan fraction is sugars (e.g., glucose) [47,65]. Finally, these sugars are used to produce
considered in Esteghlalian et al. [72], which is an assumption that must a wide variety of energy vectors such as bioethanol and biogas [44,80].
be confirmed experimentally. Finally, in both cases the stoichiometric Different yields and performances related to obtaining these com-
reaction for xylan and xylose decomposition must be balanced con- pounds, using different operating conditions as well as raw materials to
sidering the presence of water. determine the best means of production, have been reported in recent
years. In this context, a comparison between the yields obtained by
= -k1CXylan
dCXylan
different authors in terms of bioethanol, biogas and n-butanol produc-
dt
tion follows.

= k1CXylan-k2CXylose
dCXylose
dt 2.3.1. Bioethanol
Bioethanol is one of the most important energy vectors produced in
= -k2CXylose
dCInhibitors
recent years. This energy vector can be used to supply a share of the
dt
energy demand of the transport sector since bioethanol can be used as
For both approaches, the kinetic constants are a function of the an alternative fuel. Especially, second generation bioethanol is desir-
absolute temperature and acid concentration. Therefore, a modified able due to the use of lignocellulosic raw materials. Papers related to
Arrhenius expression is proposed as follows: bioethanol production using lignocellulosic biomass have been pub-
ki = ki0Cne(-Ea /RT)
lished since 1990 [81,82]. Nevertheless, more recent publications are
considered in this paper. Kuglarz et al. reported bioethanol and succinic
where ki0 is the pre-exponential factor (1/min), C is the acid con- acid production using rapeseed straw as the raw material and a dilute
centration (% w/w), n is the acid concentration exponent (1.75 for sulphuric acid pretreatment and saccharification stage λ. The acid
xylose formation and 1.0 for xylose degradation) [74], Ea is the acti- pretreatment was carried out using a 20% solids loading, 1% w/w acid
vation energy (kJ/mol) and T is the absolute temperature of the pre- concentration, 180 °C and residence time of 10 min. From this process,
treatment process. The kinetic modelling of the hemicellulosic decom- the authors reported a xylan conversion of 50% and an increase in the
position is important to perform any prediction and simulation of the glucan content in the pretreated biomass of between 48% and 53%,
acid pretreatment process. Table 4 reports the kinetics parameters which leads to obtaining high fermentable sugars concentrations in the
found by different authors for a wide variety of raw materials. saccharification stage. In fact, this process was performed using Cel-
Recent studies have been focused on the study of the mass transfer licCTec2 enzymatic complex with an enzyme loading of 64.6 FPU/g for
between the catalyst (i.e., acid) and the xylan involved in the lig- 48 h at 50 °C. The bioethanol yield at these processing conditions was
nocellulosic matrix. In fact, Chen et al. reported a novel biphasic 122 kg of bioethanol per tonne of rapeseed straw [66]. On the other
method to model the dilute acid pretreatment of corn stover [77]. In the hand, Sritrakul et al. compared the bioethanol production between
method, the diffusion coefficient of the sulphuric acid in water was used separate saccharification and fermentation (SHF) and the simultaneous
to perform the mass balances of the process using a partial difference saccharification and fermentation (SSF) of acid pretreated sugarcane
equation (PDE), which is a function of the residence time and the radius bagasse pith [83]. The acid pretreatment was carried out at 1% w/w
of the molecules. This model was correlated with experimental data, acid concentration, 10% solids loading, and 121 °C for 30 min. These
giving a good correlation. The above effort shows one attempt to im- conditions allow similar results to those reported above to be obtained.
prove the understanding of the acid pretreatment process to better In fact, a glucan recovery and xylan solubilization of 54.35% and
describe the phenomena of the process. Other efforts include the use of 86.80% were reported. Nevertheless, low bioethanol yields of 46.2 and

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J.C. Solarte-Toro, et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

66.4 kg were obtained in the case of the SHF and SSF processes, re- in this paper.
spectively. These results allow the conclusion that the SSF process gives
better yields than the SHF process, which has been demonstrated 3. Case study: olive tree biomass for bioethanol production
widely in the literature. Moreover, a comparison between the studies
allows the analysis of the effect of the pretreatment conditions and the Olive trees have traditionally been cultivated mainly in
influence of the lignocellulosic structure on the bioethanol production. Mediterranean countries, but their cultivation is now being carried out
Therefore, the importance of the optimization of the pretreatment worldwide due to the healthful properties of olive oil. In 2016, the
conditions in terms of sugars concentration and yield should be in- world surface of olive groves was more than 10 million, of which a
vestigated. Thus, Matinez-Patiño et al. optimized the dilute acid pre- quarter were located in Spain [88]. Olive tree pruning biomass (OTP) is
treatment conditions to obtain the highest possible bioethanol yield the most abundant residue among the different wastes that are gener-
using olive tree as raw material in an experimental way [33]. These ated in the whole process of olive oil production, with an estimated
authors reported that bioethanol yields of 61.9 and 42.3 kg of bioe- average generation of 1.5 tonnes per ha per year [89]. This agricultural
thanol per tonne of olive biomass are obtained when the diluted acid residue is produced every two years to remove the old and un-
process conditions are optimized to produce high sugars concentrations productive branches as well as prepare the tree for the next crop. A
and yields after the saccharification stage. In fact, the best conditions to typical lot is formed of 25% of leaves, 50% of thin branches and 25% of
perform the pretreatment of this raw material were about 160 °C, 5% thick branches or wood. This waste must be disposed of to avoid the
w/w acid concentration and solids loading of 35% for the case of a high propagation of vegetal diseases. Nowadays, OTP is eliminated by
sugars concentration and 15% for the case of a high sugars yield [33]. grinding and spreading the chips across the field to enrich the soil or by
direct burning in the fields, which can cause environmental concerns
2.3.2. Biogas [90].
In the same way as bioethanol, biogas is another important energy Several applications have been studied in order to take advantage of
vector produced in recent years. This can be used as a gaseous fuel to this lignocellulosic biomass, such as thermochemical ones for electricity
produce heat and power for both domestic and industrial use. Biogas is generation (combustion, pyrolysis or gasification) or as a natural source
composed of methane, carbon dioxide and other traces of gases such as of chemicals like lignin, antioxidants, oligosaccharides or bioethanol
hydrogen sulphide and ammonia [84]. This energy vector is produced [91]. The main components of OTP are cellulose, hemicellulose and
through the anaerobic digestion of organic matter and lignocellulosic lignin, as well as a significant amount of soluble compounds (ex-
biomass [85]. Nevertheless, the second-generation biomass degradation tractives). This extractive fraction contains sugars, organic alcohols and
needs a pretreatment to increase the biogas yields obtained from the phenolic compounds among others [92]. Therefore, this biomass has
process. In this respect, significant improvements have been reported been proposed as a raw material in a biorefinery [91].
when the acid pretreatment is included as a pretreatment stage of the Different pretreatments have been performed to obtain second
biogas production process. Sarto et al. reported on biogas production generation bioethanol from OTP biomass, such as steam explosion [93],
using the slurry from the acid pretreatment process of water hyacinth as liquid hot water [94,95], organosolv [96], inorganic salts [97] or dilute
raw material [86]. An increase in biogas production of 131.45% was acid pretreatment [33]. Moreover, the combination of various methods
recorded when the pretreatment was applied. Seeking to perform the has been tested to produce higher yields. In fact, biological followed by
pretreatment stage at the best operating conditions, these authors dilute acid pretreatment [98], acid pretreatment followed by alkaline
varied the acid concentration and the residence time to obtain the hydrogen peroxide oxidation [99], or autohydrolysis followed by or-
highest COD/N ratio. Thus, the pretreatment conditions were 121 °C, ganosolv pretreatment [100] has been applied to OTP biomass.
30 min, 5% v/v acid concentration and 10% solids loading [86]. Nevertheless, the presence of inhibitory compounds should be eval-
Moreover, Taherdanak et al. reported an increase of 15.5% in the uated before the fermentation process to avoid low yields.
biogas yield of wheat plant after acid pretreatment carried out at In order to increase the economic viability of bioethanol production,
121 °C, 60 min, 1% v/v [80]. The reported yield after the pretreatment high ethanol concentrations in liquors is an essential aspect to reduce
was 302.4 ml per gram of volatile solids, which is comparable with the distillation costs. Therefore, the use of high solid loadings in the pre-
results obtained for different raw materials such as switchgrass, empty treatment or saccharification stages as well as the use of different
fruit bunches, and rice straw, among others [85]. Nevertheless, the acid process configurations are some strategies used for this purpose. After
pretreatment process must be carried out carefully because the by- acid pretreatment of OTP, different bioconversion schemes have been
products formed during this process can have an inhibitory effect on the tested. Martinez-Patiño et al. compared the use of solid and liquid
anaerobic digestion process. This situation was evidenced when Ven- fractions separately with the enzymatic hydrolysis of whole slurry and
turin et al. analysed the results derived from the co-digestion of pre- then the co-fermentation to obtain ethanol [99]. The enzymatic hy-
treated and un-pretreated corn stalk [87]. The pretreatment conditions drolysis of the whole slurry obtained similar sugar yields to the other
applied by these authors were 0.75% v/v acid concentration, 132 °C configuration but only with a solution with a higher concentration of
and solids loading 20%. Therefore, the implementation of the acid sugars. In the fermentation step, a modified E. coli was employed to
pretreatment must be evaluated at different operating conditions to coferment hexoses and pentoses, achieving an ethanol yield of 14.4 g/
ensure there is no inhibition of the consortium of microorganisms that 100 g OTP.
carry out the digestion process. Martinez-Patiño et al. [33] performed an optimization of the acid
After this review on acid pretreatment, it was found that the impact pretreatment of OTP to maximize the concentration and amount of
of operating conditions associated to acid pretreatment on the energy, fermentable sugars that can be obtained from it. Two optimal condi-
economics and environmental aspects of any biobased process is not tions were calculated. The first optimal condition (scenario 1) ensures
well discussed in the open literature. A special interest was placed on the highest recovery of fermentable sugars using a temperature of
the operational conditions such as solids loading, acid concentration 164 °C, solids loading 15% and sulphuric acid concentration of 5.9% as
and temperature aiming to demonstrate the influence of these variables pretreatment conditions. Meanwhile, the second condition (scenario 2)
on the products obtaining (e.g., bioethanol, biogas). Nevertheless, the ensures the highest concentration of fermentable sugars when per-
impact of the operating conditions of the acid pretreatment also can forming the pretreatment at 160 °C using a solids loading of 35% and
affect the performance and productivities of the overall biobased pro- acid concentration of 4.9%. Nevertheless, these conditions do not en-
cess. To demonstrate this statement, a case of study focused on the sure the techno-economic feasibility of the bioethanol production using
influence of the solids loading into the bioethanol yields, energy con- this raw material at either pilot or industrial level. Thus, the simulation
sumption, economic indicators and environmental impact is developed and evaluation from the techno-economic perspective of the bioethanol

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J.C. Solarte-Toro, et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

Fig. 2. Bioethanol production process using olive biomass as raw material.

production using OTP as raw material considering the above-mentioned of the gypsum formed. The overliming process was carried out at 50 °C
optimal experimental conditions (scenarios 1 and 2) is performed. and 1 atm. Afterwards, the liquid fraction from this stage and the cel-
lulose-rich solid from the acid pretreatment process were mixed in the
3.1. Lignocellulosic feedstock enzyme degradation process, where the cellulose was decomposed to
glucose using an enzymatic complex. This process is carried out at pH
The olive tree pruning (OTP) considered in this work is the OTP 4.8 and 50 °C with a solids concentration not greater than 20% w/v for
described by Martínez-Patiño et al. [33]. The chemical composition of 72 h, an cellulose enzyme loading (CellicCTec3, Bagsvaerd, Denmark)
the olive tree pruning is presented by Solarte-Toro et al. [101] of 15 FPU/g of substrate and β-glucosidase (Novozyme 50010, Bags-
vaerd, Denmark) loading of 15 international units/g of substrate [6].
Then, an evaporation process was performed to increase the fermen-
3.2. Simulation procedure and process description
table sugars concentration until 110 g/l and to avoid the oversizing of
the subsequent processing stages [107]. Moreover, the concentration
The proposed process for the bioethanol production is described
stage was considered in the bioethanol production process in order to
using the main unit operations and process conditions. The simulated
maintain always the same initial conditions in the fermentation stage.
bioethanol production process consists of seven blocks, which are: ex-
Then, the fermentation process was carried out using a C5 and C6 rich
traction, pretreatment, overliming, saccharification, concentration (i.e.,
substrate such as carbon substrate for Escherichia coli MM160 geneti-
evaporation), fermentation and distillation. This production process
cally modified [33]. The operating conditions of the fermentation
was designed following the hierarchy, sequencing and integration
process were 37 °C and 1 atm, and the ethanol yield of 78%. Moreover,
concepts exposed by Moncada et al. [102]. The bioethanol production
nutrients such as diammoniumb phosphate (DAP) and potassium hy-
process using olive tree biomass can be seen as a biorefinery due to the
droxide were used to ensure the microorganism growth and the pH
possible production of antioxidants and the valorization of lignin (See
control, respectively.
Fig. 2). Nevertheless, the main analysis of the process has been focused
Finally, downstream process was designed using conceptual design
on the bioethanol yield and productivity of the process. The block
tools and the process separation scheme proposed by Humbird et al.
diagram of the bioethanol production process is presented in Fig. 2.
[108]. Thus, a set of two distillation columns and a molecular sieves
The olive biomass extraction is the first stage of the bioethanol
dehydration process were considered. The first distillation tower con-
production process. This stage is proposed to remove some inhibitory
centrates the water-ethanol mixture from the fermentation block and
compounds of the olive biomass able to reduce the bioethanol yields in
removes the entire solid fraction formed during the previous blocks
the fermentation process. Moreover, according to the hierarchy char-
(e.g., biomass). From this, the solid fraction that is removed, which is
acterization of the raw materials, the high value-added products should
rich in lignin, can be upgraded to polymers, fibres, phenols, benzene,
be extracted in the first processing stages [103]. Thus, antioxidants
toluene, and xylenes (i.e., BTX) compounds [109]. The number of
were removed due to the wide market of these components inthe
theoretical stages considered for this tower was 10 with a reflux ratio
pharmaceutical, food and cosmetic industries [104–106] In this way, a
around 1.3. The top stream from this tower is condensed and sent to a
trayed-column of two theoretical stages was simulated to remove water
rectification column to produce an azeotropic ethanol mixture (i.e.,
soluble components from the OTP biomass such as sugars (e.g., glucose,
92% w/w) at saturation conditions. Once the bioethanol has been
xylose, arabinose, and mannose), polyols (e.g., mannitol) and phenolic
purified, this stream is sent for separation with molecular sieves, where
compounds. The extraction process was carried out at 2 atm, adiabatic
this mixture is vaporized and pressurized to 118 °C and 1.43 atm [110].
conditions, using heated water at 120 °C to reach 20% solubilization of
Consequently, anhydrous ethanol (> 99.5% w/w) is produced [6].
the loaded solid. Then, the extracted material was pretreated using
dilute acid to disrupt the lignocellulosic matrix into a rich xylose liquor
and cellu-lignin fibre. The process conditions (solid–liquid ratio, tem- 3.2.1. Technical and energy assessment
perature and acid concentration) of this stage were according to the two The material balance and energy requirements of the bioethanol
experimental optimums proposed by Martínez-Patiño et al. [33]. From production process were obtained using Aspen Plus v9.0 software
this stage, the liquid fraction was detoxified. Here, two processes were (Aspen Technology Inc., USA). The process was simulated using a small-
carried out: the first one decreases the furfural, HMF, formic acid, acetic scale process with a mass flow rate of 90 OTP t/day (wet basis) as
acid and phenols (inhibitor compounds) concentrations through the feedstock (30,000 OTP t/y, 8000 h/y). As thermodynamic models to
addition of Ca(OH)2 (pH= 10). On the other hand, the second process describe the liquid and vapour phases as well as to calculate the activity
involves adjusting the pH to 4.8 using sulphuric acid and the separation and fugacity coefficients, the Non-Random Two Liquids (NRTL) and the

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Hayden–O′Connell equation of state (HOC EoS), respectively, were used Table 6

[6]. Moreover, the lignocellulosic composition of the raw material (i.e., Water consumption and liquid waste for the different process stages.
cellulose, hemicellulosic components and lignin) was introduced into Feature Scenario 1 (Solids loading Scenario 2 (Solids loading
the simulation software manually using the thermodynamic properties 15%) 35%)
reported by the National Research Energy Laboratory (NREL) [111].
Once the material balances of each stage of the bioethanol pro- Water Liquid Water Liquid waste
consume waste (kg/ consume (kg/h)
duction process were obtained, the energy requirements in terms of (kg/h) h) (kg/h)
heating and cooling were calculated. As the heat source, low (125 °C,
2.46 atm), medium (175 °C, 8.64 atm) and high (250 °C, 38.92 atm) Extraction 11,559.90 7650.54 11,559.90 7650.54
pressure steam were used. Furthermore, demineralized water (20 °C) Pretreatment 17,074.63 2854.15 7015.72 3718.89
Overliming
was employed as cooling agent. Thus, the estimation of the energy
Saccharification 974.37
consumption was performed based on the results of the energy balances Evaporation 7999.73 183.19
obtained from the simulation. In this way, the steam and cooling water Fermentation
needs in heat exchangers, reboilers and condensers were obtained. Distillation 6712.88 5551.20
Total 28,634.53 25,217.29 19,549.99 17,103.81
Finally, the simulation tool Aspen Energy Analyzer v.9.0 was used to
perform the pinch analysis of the process using hot and cold streams in
the process to reduce the amount of utilities employed in the process,
that shows the biggest difference is the calcium hydroxide used in the
which is directly related to the energy integration [112].
overliming, which is close to double, followed by water with a con-
sumption almost 50% higher (> 9000 kg/h) and, thirdly, the sulphuric
3.2.2. Economic and environmental assessment acid used in the pretreatment and overliming, with 35% higher. The
The economic assessment of the bioethanol production process in- obtained bioethanol yields for the first and second optimal conditions
volves the calculation of yields, economic parameters and costs asso- were 110.83 kg bioethanol/t raw material and 97.30 kg bioethanol/t
ciated with the capital and operational expenditures. To evaluate the raw material (139.45–122.43 l/t respectively). These yields show that
performance of the process, the bioethanol yield was calculated [101]. scenario 1, which has the highest amount of fermentable sugars, pro-
Instead, the production costs was calculated and compared to the cur- duces more bioethanol than scenario 2. The yields obtained using OTP
rent bioethanol market prices. Moreover, the utilities costs, total pro- biomass are very similar to that reported for other lignocellulosic
duction costs and the total project capital costs are reported. These costs feedstocks such as the forestry residues hog fuel, with 100 kg bioe-
were calculated using the commercial software Aspen Process Eco- thanol/t. They are higher than empty fruit bunches (EFB) or sugarcane
nomic Analyzer v9.0 (Aspen Technology Inc., USA) using the mass and bagasse (SCB), which are 80.41 kg/t and 59.26 kg/t, respectively [92],
energy balances from the simulations. The economic evaluation of the and lower than other forestry residues such as tops and branches or
process was carried out in the Spanish context. Therefore, an annual early thinnings, with 172 kg/t and 188 kg/t [40] and non-lig-
interest rate of 5% was considered. Moreover, the operator and super- nocellulosic feedstocks such as brown algae with 239.03 kg/t [41].
visor labour costs were 22.84 USD/h and 24.69 USD/h, respectively Scenario 1 consumes more water than scenario 2 (i.e. 68.89 kg
[113]. Finally, the capital depreciation method and the tax rate as well water/kg bioethanol and 53.58 kg water/kg bioethanol). The biggest
as the operation plant of the facility reported by Solarte-Toro et al. difference is in the acid pretreatment stage, with more than 10,000 kg/
[101] were used. h (Table 6). If the extraction stage is not considered, the values are
41.08 kg water/kg bioethanol and 21.89 kg water/kg bioethanol, this
3.3. Results and discussion last value being similar to those reported for corn stover
15.08–25.48 kg water/kg bioethanol [42]. In the case of scenario 2,
3.3.1. Bioethanol yields and process requirements there is a water consumption in the saccharification stage to adjust to
The flows of raw materials and bioethanol produced are shown in the maximum solid–liquid ratio used of 20% w/v [43]. In the same
Table 5. This shows that almost all flows are greater in scenario 1 ex- way, the specific liquid waste generated by using a low solids loading is
cept for the enzymes flow, which is very similar, and the potassium high. Specifically, scenario 1 (i.e. solids loading of 15%) produces
hydroxide, which is half. The OTP/enzymes ratio of near 20 is very 60.67 kg effluent/kg bioethanol and scenario 2 (i.e. solids loading of
similar to that reported for different forestry residues [40]. The input 35%) produces 46.88 kg effluent/kg bioethanol, which is 77%. In the
case of scenario 1, the greatest effluent is produced in the evaporation
Table 5 stage, approx. 8000 kg/h, more than 40 times higher than that pro-
Mass balance of the bioethanol production process. duced in scenario 2. For this latter, the highest effluent is produced in
Feature Scenario 1 (Solids loading Scenario 2 (Solids loading the distillation stage, with 5551.20 kg/h, lower than that produced in
15%) 35%) scenario 1, representing less than 83%. In the pretreatment stage, a
greater effluent is produced in scenario 2 due to the washing of the solid
Raw Products Raw Products since there is a greater recovery of it (see Table 6). In summary, sce-
materials (kg/h) materials (kg/h)
(kg/h) (kg/h)
nario 1 produces almost 50% more liquid waste than scenario 2.
Scenario 1 with the lowest load of solid (15%) has the highest
Olive tree pruning 3750.00 3750.00 specific consumption of utilities (heating+cooling) with 59.55 kW/(kg
Water 28,634.53 19,549.99 bioethanol/h), more than twice the case with high load (28.05 kW/(kg
Sulphuric acid 261.40 193.82
bioethanol/h)). This behaviour is similar to that found by Rodriges
Calcium 187.57 109.48
hydroxide et al. [44] when evaluating different pretreatments with corn stover.
Enzymes 219.03 221.93 The stage with the highest consumption of utilities in scenario 1 is
Diammonium 3.20 2.81 evaporation, due to the low concentration of sugars in the liquor pro-
phosphate
duced, representing more than 50% of the total consumed utilities,
E. coli MM160 4.99 4.38
Potassium 14.20 30.53 followed by the pre-treatment stage with 23.57% for the highest mass
hydroxide treated (Table 7).
Protein 11.39 10.00 On the contrary, the evaporation stage in scenario 2 does not reach
Bioethanol 415.61 364.87 15% of its total consumed of utilities, and, with respect to scenario 1,

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Table 7 (Table 8). On the contrary, the evaporation stage in scenario 2 does not
Heating and cooling for the different process stages. reach 11% of its total consumption of utilities, and, with respect to
Feature Scenario 1 (Solids loading Scenario 2 (Solids loading scenario 1, less than 11%. Regarding distillation, it presents similar
15%) 35%) values in both scenarios, being higher for the case with 35% solid. In
scenario 2, the distillation is the stage with the highest emissions, more
Heating+cooling % Heating+cooling % than 29%, followed by the fermentation stage, representing almost 24%
(kW) (kW)
of the total, where the CO2 is formed in the fermentation of the sugars
Extraction 2148.86 8.68 2148.94 20.99 (Table 8). The energy integration of the process in both cases allows a
Pretreatment 5833.58 23.57 2344.91 22.91 very significant reduction in emissions, being higher in the case of
Overliming 266.07 1.08 142.77 1.39 scenario 1 (> 30%, optimum 2 > 25%). With energy integration, the
Saccharification 37.16 0.15 70.22 0.69
specific emissions of CO2 are reduced to remain at: 5.54 kg/kg bioe-
Evaporation 12,654.45 51.13 1485.90 14.52
Fermentation 152.93 0.62 148.00 1.45 thanol in scenario 1 and 3.07 kg/kg bioethanol in scenario 2, 55% of
Distillation 3656.26 14.77 3895.64 38.06 the value of scenario 1.
Total 24,749.32 100.00 10,236.38 100.00 The reduction of carbon dioxide emissions from the ethanol pro-
With energy 16,304.52 65.88 6572.25 64.20
duction process has positive environmental implications due to these
integration
ones can be considered as a starting point to implement economic in-
centives. In addition, the reduction of greenhouse gas emissions is in
less than 12%. As for the distillation, it presents similar values in both line to the global objectives of climate change, which have served as a
scenarios, being higher for the case with 35% solid. Thus in scenario 2, fundamental basis for the implementation of renewable energy projects
distillation is the stage with the highest consumption of utilities, over in developed and developing countries. From this, different policies can
38%, followed also by pretreatment as it happened in scenario 1, re- be proposed to increase the use of renewable resources.
presenting almost 23% of the total, a value very similar to scenario 1.
The decrease in the consumption of utilities in the distillation stage due 3.3.3. Economic analysis
to an increase in the sugars concentration in the liquor is much lower The economic evaluation of both scenarios is shown in Table 9.
than the increase in the utilities to carry out said concentration in the From this, it is possible to observe that the total production cost of
evaporation stage, which is in agreement with other authors [45]. scenario 1 is more than 14% higher than scenario 2 with a value of
The process energy integration in both cases allows a very sig- 10.75 million USD/y, and that the two most representative costs can be
nificant utilities saving, around 35%, being slightly higher in the case of attributed to the raw material and depreciation, around 31% and 18%,
scenario 2 (Table 7). With energy integration, the specific consumption respectively. These two costs have been reported as more influential
of utilities is reduced, remaining at 39.23 kW/(kg bioethanol/h) in factors in the production of bioethanol [46]. In both scenarios the
scenario 1 and 18.01 kW/(kg bioethanol/h) in scenario 2, this being variable costs distribution is similar. However, in the case of scenario 1,
less than half of scenario 1. This last value is of the order of that ob- the third cost is utilities followed by operating labour (17.30% and
tained for hog fuel which, as mentioned previously, had a very similar 13.41%), while for scenario 2 this order is reversed (11.50% and
yield of bioethanol [40] 15.53%). The utility costs in scenario 1 are 72% higher than scenario 2
due to the amount of liquid used in this process, which increases the
energy consumption in the scenario with low solids loading. When the
3.3.2. Carbon dioxide emissions process energy integration is realized, in both cases the annual pro-
On the other hand, a high level of carbon dioxide emissions from the duction cost is reduced, but more significantly in scenario 1 with a
fermentation stage and steam production are expected from scenario 1 reduction of more than 4%, while in scenario 2 it does not reach 2%.
due to the higher amount of sugars that are fermented and the liquid Despite this greater reduction, scenario 1 still has the highest produc-
employed in the process. In accordance with the above results, the first tion cost with 10.29 million USD/y, almost 12% higher than the value
scenario has the highest environmental impact, which can be seen as a
drawback. The specific emissions of CO2 are 7.91 and 4.22 kg/kg Table 9
bioethanol for scenario 1 and 2, respectively (close to double). The Techno-economic assessment results.
stage with the highest emissions in scenario 1 is evaporation, due to the
Feature Scenario 1 (Solids loading Scenario 2 (Solids loading
high energy requirement for the concentration of the liquor produced, 15%) 35%)
representing more than 44% of the total emissions produced, followed
by the pre-treatment stage with 20.58% for the largest mass treated Thousands (%) Thousands (%)
USD/year USD/year
Table 8
Raw materials 3187.97 29.67 3074.34 32.72
Carbon dioxide emissions for the different process stages. Utilities 1858.76 17.30 1080.51 11.50
Feature Scenario 1 (Solids loading Scenario 2 (Solids loading Operating labour 1440.72 13.41 1440.72 15.33
15%) 35%) Maintenance 379.00 3.53 256.00 2.72
Operating charges 360.18 3.35 360.18 3.83
Steam Fermentation Steam Fermentation Plant overhead 909.86 8.47 848.36 9.03
production (kg CO2/h) production (kg CO2/h) G and A costsa 648.02 6.03 563.17 5.99
(kg CO2/h) (kg CO2/h) Depreciation 1960.50 18.25 1772.78 18.87
Total production cost 10,745.01 100.00 9396.05 100.00
Extraction 316.08 316.08 Total production 10,287.67 95.74 9209.41 98.01
Pretreatment 676.67 235.16 costb
Overliming 0.14 0.08 Total Project Capital 24.51 22.16
Saccharification 8.80 16.62 Cost (M. USD)
Evaporation 1453.11 159.24 Bioethanol cost 2.55 2.54
Fermentation 416.00 365.22 (USD/l)
Distillation 416.40 446.71 Bioethanol cost 2.44 2.49
Total 2871.18 416.00 1173.88 365.22 (USD/l)
With energy 1884.49 416.00 754.22 365.22
a
integration General and Administrative costs.
b
With energy integration.

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J.C. Solarte-Toro, et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

of scenario 2. Moreover, the total project capital costs of scenario 1 and For each of these parameters, two values were studied, classifying them
scenario 2 were 24.51 million USD and 22.16 million USD, more than into near and middle term according to how soon they could be
10% higher in the case of scenario 1, which initially suggests that a high achieved [49]. For the near-term case, a reduction of 40% with respect
solids loading in the pretreatment stage must be used. These costs are to the base case values is proposed in the parameters "OTP cost", "en-
low compared to the data reported by Humbird et al. [108] for a facility zyme cost", “pretreatment sugars loss” and “overliming sugars loss”; an
that only produces bioethanol from corn stover. Nevertheless, this dif- increase in the conversions in the saccharification (glucan-glucose en-
ference between the reported and the obtained data is attributed to the zymatic conversion) and the fermentation (sugars-ethanol conversion)
process scale, which is very low in this work. Compared to a closer scale up to values of 0.8 and 0.85 respectively, and finally an increase in the
of 80,000 t/y, the value is quite similar, with 29.9 million USD [41]. life of the plant up to 20 years for the calculation of depreciation. On
The bioethanol production cost for both scenarios was almost the the other hand, a reduction of 60% is proposed for the medium term
same if energy integration is not done, being lower in the case of sce- with respect to the base case values in the parameters "OTP cost",
nario 2 with a value of 2.54 USD/l. However, with energy integration, "enzyme cost", “pretreatment sugars loss” and “overliming sugars loss”;
scenario 1 has the lowest value with 2.44 USD/l since the value has an increase in the conversions in saccharification and fermentation to
been reduced by 0.11 USD/l, while in the case of scenario 2 it has only values of 0.95 and 0.92 respectively, and finally an increase in the life
reduced by 0.05 USD/l, where the utilities cost had a lower influence on of the plant up to 30 years for the calculation of depreciation.
the final value. In any case, the value obtained under the conditions The results obtained for both cases are shown in Fig. 4. For the
studied (small scale, current prices of raw materials such as olive "near-term" case in scenario 1 the parameter that allows the greatest
pruning, and enzymes) is greater than the current market value of reduction is depreciation, with a value of 0.23 USD/l, followed very
bioethanol, which can be of the order of 0.52 USD/l [47]. The above closely by “pretreatment sugars loss” and “sugars-ethanol conversion”
values are in the order of those found for other pretreatments with corn with 0.2 and 0.19 USD/l respectively (Fig. 4(a)). For scenario 2, these 3
stover in different conditions: 1.78–2.46 USD/l for LHW and 1.80–3.56 parameters are also the ones that offer the greatest reductions, but the
USD/l for AFEX, but with a much larger plant size, greater than 2000 t/ order is different and with higher values (“pretreatment sugars loss”,
day [44]; and higher than for different forestry residues pretreated with “depreciation”, “sugars-ethanol conversion”, with 0.27, 0.24 and 0.20
steam explosion 0.77–1.52 USD/l, also with a higher plant size 600 t/ USD/l respectively) (Fig. 4(b)). In both cases, if the costs of the OTP and
day [40]. enzymes are shown together, this would present the second largest
The bioethanol production cost is the main cost in raw materials reduction, with values of 0.21 and 0.25 USD/l for scenario 1 and sce-
(around 30%) and among these in both scenarios the order of the three nario 2 respectively.
highest is OTP, enzymes and water, which together accumulate more For the "medium-term" case with respect to "near-term”, the order of
than 86% (Fig. 3). The first two, OTP and enzymes, represent more than the parameters is altered in the reduction that could be achieved. For
72% of the cost of raw materials, with values higher than 37% and 34% scenario 1 now the parameter that achieves the greatest reduction is
respectively. The cost of bioethanol has been correlated with the price “sugars-ethanol conversion” (0.37 USD/l) with three other parameters
of the feedstock and the cost of the enzyme [46], the largest con- with very similar values: depreciation, “glucan-glucose enzymatic
tributor. The costs of these last two would need to be reduced, in the conversion” and “pretreatment sugars loss” (0.31, 0.31 and 0.28 USD/
case of OTP, looking for an optimal location of the plant, which could l), to which could be added the sum of the costs of the OTP and enzymes
reduce the logistic costs (production and transport), while for enzymes (0.33 USD/l). For scenario 2, “pretreatment sugars loss” still has the
in recent years there have been major reductions in the cost of pro- highest reduction (0.39 USD/l), but the order of the other parameters
duction along with increases in their enzymatic capacity, so it would changes, resulting in “sugars-ethanol conversion” below (0.37 USD/l)
also be possible to lower the dosage [48]. and “glucan-glucose enzymatic conversion” and depreciation very close
(0.33, 0.32 USD/l); the sum of the costs of the OTP and enzymes would
tie in second place. In all cases the “overliming sugars loss” has the
3.4. Sensitivity analysis lowest reductions.
Finally, if all the reductions obtained for the "near-term" case could
A sensitivity analysis of the production cost of bioethanol was car- be achieved, reductions greater than 40% would be achieved, with
ried out in which the influence of 7 key parameters was studied. On the values of the ethanol production cost of 1.44 and 1.37 USD/l for sce-
one hand, there would be the costs of raw materials with greater in- nario 1 and scenario 2, respectively, still far from the current market
fluence such as OTP and enzymes. Moreover, there would be sugar value. On the other hand, making the same consideration for the
losses in the pretreatment and overliming stages and conversions in "medium-term", the reductions are close to duplicating the previous
saccharification (glucan-glucose enzymatic conversion) and fermenta- ones, leaving values of 0.77 and 0.63 USD/l for scenario 1 and scenario
tion (sugars-ethanol conversion), the last four relative to the ethanol 2, already in the order of the current values of the market. It should be
production yield. Finally there is depreciation, since this was shown as noted that scenario 2 is more affected by all the parameters studied,
the second most representative cost after the raw materials (Table 9).

Fig. 3. Distribution of raw materials cost: a) Optimum 1 (solids loading 15%). b) Optimum 2 (solids loading 35%).

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J.C. Solarte-Toro, et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

Fig. 4. Results of the sensitivity analysis for the key process parameters in near- and medium-term (base case values between parentheses). a) Scenario 1 (solids
loading 15%). b) Scenario 2 (solids loading 35%).

since the greatest reductions are obtained in both scenarios and reduce the environmental impact. Nevertheless, the conversion of the
therefore the lower costs of bioethanol production. bioethanol process to a biorefinery using the properties of the olive tree
biomass to obtain antioxidants and lignin should be performed to de-
crease the production costs. Another option to reduce the high bioe-
4. Practical implications of this study
thanol costs is the opportunity to cogenerate the solid residues from the
process to decrease the utilities costs of the process.
The acid pretreatment as pretreatment technology is susceptible to
be improved changing different parameters related to the operating
Acknowledgements
conditions as well as the reactor configuration. This review can serve as
a basis to know some of the most recent ways used to perform this
The authors express their gratitude to the Universidad de Jaén and
pretreatment as well as the most representative raw materials tested
the Universidad Nacional de Colombia – Sede Manizales.
under acidic conditions. In this way, a wide variety of research ideas
can be extracted from this paper (e.g., the use of a solid catalyst to
Conflict of interest
perform the pretreatment process, the research of the best operating
conditions to perform the pretreatment of new feedstocks and so forth).
The authors declare that they do not have potential conflict of in-
On the other hand, the case of study can serve as a guide to observe the
terests
impact that the acid pretreatment has on the overall performance of a
production process. Moreover, the case of study can serve to understand
Financial support
the effect of the acid pretreatment process design in the sustainability of
a transformation process. Finally, this study can be used as a base able
This work has been partially financed by the Spanish Ministerio de
to be considered before the implementation of the acid pretreatment.
Economía y Competitividad (Ref. ENE2017-85819-C2-1-R. including
FEDER funds). Solarte-Toro and Cardona-Alzate have been partially
5. Conclusions financed by Departamento Administrativo de Ciencia, Tecnología e
Innovación (Colciencias. grant number 761 Jóvenes Investigadores)
The acid pretreatment process has a wide variety of conditions to and the Facultad de Ingeniería y Arquitectura of the Universidad
perform the upgrading of lignocellulosic biomass. Nevertheless, the best Nacional de Colombia at Manizales (grant number 206010012730).
operation conditions need to be determined for a specific raw material. Romero-García gratefully acknowledges the postdoctoral scholarship
On the other hand, the acid pretreatment process has been improved in received from Junta de Andalucía.
terms of economic and environmental aspects. For this, the use of in-
novative processes such as the dry dilute acid pretreatment and the use References
of solid catalyst is an alternative to enhance the performance of the
process. Moreover, optimization methods and statistical studies must be [1] Ghaffarianhoseini A, Dahlan ND, Berardi U, Ghaffarianhoseini A, Makaremi N,
included in the calculation of the best operating conditions. With re- Ghaffarianhoseini M. Sustainable energy performances of green buildings: a review
of current theories, implementations and challenges. Renew Sustain Energy Rev
spect to the case study, the pretreatment process conditions have a high 2013;25:1–17. https://doi.org/10.1016/j.rser.2013.01.010.
influence on the final bioethanol yield as well as the liquid, solid and [2] Abdmouleh Z, Alammari RAM, Gastli A. Review of policies encouraging renewable
gaseous releases. Therefore, a high solids loading is recommended to energy integration & best practices. Renew Sustain Energy Rev 2015;45:249–62.

12
J.C. Solarte-Toro, et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

https://doi.org/10.1016/j.rser.2015.01.035. Chemical and physicochemical pretreatment of lignocellulosic biomass : a review.

[3] Demírbas A. Bioethanol from cellulosic materials: a renewable motor fuel from Enzyme Res 2011. https://doi.org/10.4061/2011/787532.
biomass. Energy Sources 2005;27:327–37. https://doi.org/10.1080/ [31] Triana CF, Quintero JA, Agudelo RA, Cardona CA, Higuita JC. Analysis of coffee
00908310390266643. cut-stems (CCS) as raw material for fuel ethanol production. Energy
[4] Lieder M, Rashid A. Towards circular economy implementation: a comprehensive 2011;36:4182–90. https://doi.org/10.1016/j.energy.2011.04.025.
review in context of manufacturing industry. J Clean Prod 2016;115:36–51. [32] López-Linares JC, Cara C, Moya M, Ruiz E, Castro E, Romero I. Fermentable sugar
https://doi.org/10.1016/j.jclepro.2015.12.042. production from rapeseed straw by dilute phosphoric acid pretreatment. Ind Crops
[5] Prasara-A J, Gheewala SH. Sustainable utilization of rice husk ash from power Prod 2013;50:525–31. https://doi.org/10.1016/j.indcrop.2013.08.028.
plants: a review. J Clean Prod 2016;167:1020–8. https://doi.org/10.1016/j. [33] Martínez-Patiño JC, Romero I, Ruiz E, Cara C, Romero-García JM, Castro E. Design
jclepro.2016.11.042. and optimization of sulfuric acid pretreatment of extracted olive tree biomass
[6] Cardona Alzate CA, Solarte-Toro JC, Peña ÁG. Fermentation, thermochemical and using response surface methodology. BioResources 2017;12:1779–97. https://doi.
catalytic processes in the transformation of biomass through efficient biorefineries. org/10.15376/biores.12.1.1779-1797.
Catal Today 2018;302:61–72. https://doi.org/10.1016/j.cattod.2017.09.034. [34] Cara C, Ruiz E, Oliva JM, Sáez F, Castro E. Conversion of olive tree biomass into
[7] Intenrational Energy Agency. Global Energy & CO2 Status Report 2017:1–15; fermentable sugars by dilute acid pretreatment and enzymatic saccharification.
2018. Bioresour Technol 2008;99:1869–76. https://doi.org/10.1016/J.BIORTECH.2007.
[8] Renewable energy policy network for the 21st century (REN21). Renewables 2017 03.037.
global status report. Paris Renew Energy Policy Netw 21st Century:325. doi:978-3- [35] He Y, Zhang J, Bao J. Dry dilute acid pretreatment by co-currently feeding of corn
9818911-3-3; 2018. stover feedstock and dilute acid solution without impregnation. Bioresour Technol
[9] British Petroleoum (BP). Statistical Review of World Energy. London, UK 2014;158:360–4. https://doi.org/10.1016/j.biortech.2014.02.074.
2018:1–53; 2018. [36] Qi W, He C, Wang Q, Liu S, Yu Q, Wang W, et al. Carbon-based solid acid pre-
[10] Triantafylidis K, Lappas A, Stocker M. The role of catalysis for the sustainable treatment in corncob saccharification : specific xylose production and efficient
production of bio-fuels and bio-chemicals. 1st ed. Amsterdam, The Netherlands: enzymatic hydrolysis. ACS Sustain Chem Eng 2018. https://doi.org/10.1021/
Elsevier B.V; 2013. ISSN (Hardcover): 9780444563309. ISBN (e-book): acssuschemeng.7b03959.
9780444563323. [37] Miller S, Hester R. Concentrated acid conversion of pine softwood to sugar. Part 1:
[11] Kummamuru B. WBA global bioenergy statistics 2017. 4th ed. World Bioenergy use of a twin-screw reactor for hydrolysis pretreatment. Chem Eng Commun
Association; 2017. https://doi.org/10.1016/0165-232X(80)90063-4. 2007;194:85–102. https://doi.org/10.1080/00986440600586545.
[12] Rincón LE, Becerra LA, Moncada J, Cardona CA. Techno-economic analysis of the [38] Behera S, Arora R, Nandhagopal N, Kumar S. Importance of chemical pretreatment
use of fired cogeneration systems based on sugar cane bagasse in south eastern and for bioconversion of lignocellulosic biomass. Renew Sustain Energy Rev
mid-western regions of Mexico. Waste Biomass- Valoriz 2014;5:189–98. https:// 2014;36:91–106. https://doi.org/10.1016/j.rser.2014.04.047.
doi.org/10.1007/s12649-013-9224-0. [39] Zhou C-H, Xia X, Lin C-X, Tong D-S, Beltramini J. Catalytic conversion of lig-
[13] Maltsoglou I, Kojakovic A, Rincón LE, Felix E, Branca G, Valle S, et al. Combining nocellulosic biomass to fine chemicals and fuels. Chem Soc Rev
bioenergy and food security: an approach and rapid appraisal to guide bioenergy 2011;40:5588–617. https://doi.org/10.1039/c1cs15124j.
policy formulation. Biomass- Bioenergy 2014;79:80–95. https://doi.org/10.1016/ [40] Janga KK, Hägg M-B, Moe ST. Influence of acid concentration, temperature, and
j.biombioe.2015.02.007. time on the concentrated sulfuric acid hydrolysis of pinewood and aspenwood: a
[14] Ang BW, Choong WL, Ng TS. Energy security: definitions, dimensions and indexes. statistical approach. BioResources 2011;7:0391–411. https://doi.org/10.15376/
Renew Sustain Energy Rev 2015;42:1077–93. https://doi.org/10.1016/j.rser. biores.7.1.0391-0411.
2014.10.064. [41] Liu Q, Li W, Ma Q, An S, Li M, Jameel H, et al. Pretreatment of corn stover for
[15] Moncada J, Tamayo J, Cardona CA. Evolution from biofuels to integrated bior- sugar production using a two-stage dilute acid followed by wet-milling pretreat-
efineries: techno-economic and environmental assessment of oil palm in Colombia. ment process. Bioresour Technol 2016;211:435–42. https://doi.org/10.1016/j.
J Clean Prod 2014;81:51–9. https://doi.org/10.1016/j.jclepro.2014.06.021. biortech.2016.03.131.
[16] Moncada J, Cardona CA, Higuita JC, Vélez JJ, López-Suarez FE. Wood residue [42] Ask M, Olofsson K, Di Felice T, Ruohonen L, Penttilä M, Lidén G, et al. Challenges
(Pinus patula bark) as an alternative feedstock for producing ethanol and furfural in enzymatic hydrolysis and fermentation of pretreated Arundo donax revealed by
in Colombia: experimental, techno-economic and environmental assessments. a comparison between SHF and SSF. Process Biochem 2012;47:1452–9. https://
Chem Eng Sci 2016;140:309–18. https://doi.org/10.1016/j.ces.2015.10.027. doi.org/10.1016/j.procbio.2012.05.016.
[17] Kumar A, Samadder SR. A review on technological options of waste to energy for [43] Chiranjeevi T, Mattam AJ, Vishwakarma KK, Uma A, Peddy VCR, Gandham S,
effective management of municipal solid waste. Waste Manag 2017;69:407–22. et al. Assisted single-step acid pretreatment process for enhanced delignification of
https://doi.org/10.1016/j.wasman.2017.08.046. rice straw for bioethanol production. ACS Sustain Chem Eng 2018;6:8762–74.
[18] Gaurav N, Sivasankari S, Kiran GS, Ninawe A, Selvin J. Utilization of bioresources https://doi.org/10.1021/acssuschemeng.8b01113.
for sustainable biofuels: a review. Renew Sustain Energy Rev 2017;73:205–14. [44] Satari Baboukani B, Vossoughi M, Alemzadeh I. Optimisation of dilute-acid pre-
https://doi.org/10.1016/j.rser.2017.01.070. treatment conditions forenhancement sugar recovery and enzymatic hydrolysis of
[19] Tian SQ, Zhao RY, Chen ZC. Review of the pretreatment and bioconversion of wheat straw. Biosyst Eng 2012;111:166–74. https://doi.org/10.1016/j.
lignocellulosic biomass from wheat straw materials. Renew Sustain Energy Rev biosystemseng.2011.11.009.
2018;91:483–9. https://doi.org/10.1016/j.rser.2018.03.113. [45] Avci A, Saha BC, Dien BS, Kennedy GJ, Cotta MA. Response surface optimization of
[20] Chiaramonti D, Prussi M, Ferrero S, Oriani L, Ottonello P, Torre P, et al. Review of corn stover pretreatment using dilute phosphoric acid for enzymatic hydrolysis
pretreatment processes for lignocellulosic ethanol production, and development of and ethanol production. Bioresour Technol 2013;130:603–12. https://doi.org/10.
an innovative method. Biomass- Bioenergy 2012;46:25–35. https://doi.org/10. 1016/j.biortech.2012.12.104.
1016/j.biombioe.2012.04.020. [46] Neureiter M, Danner H, Thomasser C, Saidi B, Braun R. Dilute-acid hydrolysis of
[21] Daza Serna LV, Orrego Alzate CE, Cardona Alzate CA. Supercritical fluids as a sugarcane bagasse at varying conditions. Appl Biochem Biotechnol
green technology for the pretreatment of lignocellulosic biomass. Bioresour 2002;98–100:49–58. https://doi.org/10.1385/ABAB:98-100:1-9:49.
Technol 2016;199:113–20. https://doi.org/10.1016/j.biortech.2015.09.078. [47] Díaz-Blanco DI, de La Cruz JR, López-Linares JC, Morales-Martínez TK, Ruiz E,
[22] Chen H, Liu J, Chang X, Chen D, Xue Y, Liu P, et al. A review on the pretreatment Rios-González LJ, et al. Optimization of dilute acid pretreatment of Agave lechu-
of lignocellulose for high-value chemicals. Fuel Process Technol guilla and ethanol production by co-fermentation with Escherichia coli MM160.
2017;160:196–206. https://doi.org/10.1016/j.fuproc.2016.12.007. Ind Crops Prod 2018;114:154–63. https://doi.org/10.1016/j.indcrop.2018.01.
[23] Zheng Y, Zhao J, Xu F, Li Y. Pretreatment of lignocellulosic biomass for enhanced 074.
biogas production. Prog Energy Combust Sci 2014;42:35–53. https://doi.org/10. [48] Gonzales RR, Kim JS, Kim SH. Optimization of dilute acid and enzymatic hydro-
1016/j.pecs.2014.01.001. lysis for dark fermentative hydrogen production from the empty fruit bunch of oil
[24] Yoon SY, Kim BR, Han SH, Shin SJ. Different response between woody core and palm. Int J Hydrog Energy 2018:1–12. https://doi.org/10.1016/j.ijhydene.2018.
bark of goat willow (Salix caprea L.) to concentrated phosphoric acid pretreatment 08.022.
followed by enzymatic saccharification. Energy 2015;81:21–6. https://doi.org/10. [49] Ruiz E, Romero I, Moya M, Cara C, Vidal JD, Castro E. Dilute sulfuric acid pre-
1016/j.energy.2014.11.006. treatment of sunflower stalks for sugar production. Bioresour Technol
[25] Young DM, Cabezas H. Designing sustainable processes with simulation: the waste 2013;140:292–8. https://doi.org/10.1016/j.biortech.2013.04.104.
reduction (WAR) algorithm. Comput Chem Eng 1999;23:1477–91. https://doi. [50] Tan IS, Lee KT. Solid acid catalysts pretreatment and enzymatic hydrolysis of
org/10.1016/S0098-1354(99)00306-3. macroalgae cellulosic residue for the production of bioethanol. Carbohydr Polym
[26] Jönsson LJ, Martín C. Pretreatment of lignocellulose: formation of inhibitory by- 2015;124:311–21. https://doi.org/10.1016/j.carbpol.2015.02.046.
products and strategies for minimizing their effects. Bioresour Technol [51] Lin Y-C, Huber GW. The critical role of heterogeneous catalysis in lignocellulosic
2016;199:103–12. https://doi.org/10.1016/j.biortech.2015.10.009. biomass conversion. Energy Environ Sci 2009;2:68. https://doi.org/10.1039/
[27] Hoon-Jung Y, Heon-Kim K. Acidic pretreatment. Pretreat Biomass- Process b814955k.
Technol 2015:27–50. [52] Zhang J, Wang X, Chu D, He Y, Bao J. Dry pretreatment of lignocellulose with
[28] He Y, Zhang L, Zhang J, Bao J. Helically agitated mixing in dry dilute acid pre- extremely low steam and water usage for bioethanol production. Bioresour
treatment enhances the bioconversion of corn stover into ethanol. Biotechnol Technol 2011;102:4480–8. https://doi.org/10.1016/j.biortech.2011.01.005.
Biofuels 2014;7. https://doi.org/10.1186/1754-6834-7-1. [53] Zhou PP, Meng J, Bao J. Fermentative production of high titer citric acid from corn
[29] Alvira P, Tomás-Pejó E, Ballesteros M, Negro MJ. Pretreatment technologies for an stover feedstock after dry dilute acid pretreatment and biodetoxification.
efficient bioethanol production process based on enzymatic hydrolysis: a review. Bioresour Technol 2017;224:563–72. https://doi.org/10.1016/j.biortech.2016.11.
Bioresour Technol 2010;101:4851–61. https://doi.org/10.1016/j.biortech.2009. 046.
11.093. [54] Shao S, Zhang J, Bao J. Reduction of reactor corrosion by eliminating liquid-phase
[30] Brodeur G, Yau E, Badal K, Collier J, Ramachandran KB, Ramakrishnan S. existence in dry dilute acid pretreatment of corn stover. Energy Fuels

13
J.C. Solarte-Toro, et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

2017;31:6140–4. https://doi.org/10.1021/acs.energyfuels.7b00446. pretreatment on biogas production form wheat plant. Int J Green Energy
[55] Hsu TC, Guo GL, Chen WH, Hwang WS. Effect of dilute acid pretreatment of rice 2016;13:1129–34. https://doi.org/10.1080/15435075.2016.1175356.
straw on structural properties and enzymatic hydrolysis. Bioresour Technol [81] Jarbezki A. Modelling of oscillatory behaviour in continuous ethanol fermentation.
2010;101:4907–13. https://doi.org/10.1016/j.biortech.2009.10.009. Biotechnol Lett 1992;14.
[56] Sahoo D, Ummalyma SB, Okram AK, Pandey A, Sankar M, Sukumaran RK. Effect of [82] Wyman CE. Ethanol from lignocellulosic biomass: technology, economics, and
dilute acid pretreatment of wild rice grass (Zizania latifolia) from Loktak Lake for opportunities. Bioresour Technol 1994;50:3–15. https://doi.org/10.1016/0960-
enzymatic hydrolysis. Bioresour Technol 2018;253:252–5. https://doi.org/10. 8524(94)90214-3.
1016/j.biortech.2018.01.048. [83] Sritrakul N, Nitisinprasert S, Keawsompong S. Evaluation of dilute acid pretreat-
[57] Martínez-Patiño JC, Lu-Chau TA, Gullón B, Ruiz E, Romero I, Castro E, et al. ment for bioethanol fermentation from sugarcane bagasse pith. Agric Nat Resour
Application of a combined fungal and diluted acid pretreatment on olive tree 2017;51:512–9. https://doi.org/10.1016/j.anres.2017.12.006.
biomass. Ind Crops Prod 2018;121:10–7. https://doi.org/10.1016/j.indcrop.2018. [84] Deublein D, Steinhauser A. Biogas from waste and renewable resources: an in-
04.078. troduction. Federal Republic of Germany: Wiley; 2010. ISBN (online):
[58] Castro E, Nieves IU, Mullinnix MT, Sagues WJ, Hoffman RW, Fernández-Sandoval 9783527632794 . DOI: 10.1002/9783527632794.
MT, et al. Optimization of dilute-phosphoric-acid steam pretreatment of [85] Solarte-Toro JC, Chacón-Pérez Y, Cardona-Alzate CA. Evaluation of biogas and
Eucalyptus benthamii for biofuel production. Appl Energy 2014;125:76–83. syngas as energy vectors for heat and power generation using lignocellulosic
https://doi.org/10.1016/j.apenergy.2014.03.047. biomass as raw material. Electron J Biotechnol 2018;33:52–62. https://doi.org/
[59] de Vasconcelos SM, Santos AMP, Rocha GJM, Souto-Maior AM. Diluted phosphoric 10.1016/j.ejbt.2018.03.005.
acid pretreatment for production of fermentable sugars in a sugarcane-based [86] Sarto S, Hildayati R, Syaichurrozi I. Effect of chemical pretreatment using sulfuric
biorefinery. Bioresour Technol 2013;135:46–52. https://doi.org/10.1016/j. acid on biogas production from water hyacinth and kinetics. Renew Energy
biortech.2012.10.083. 2019;132:335–50. https://doi.org/10.1016/J.RENENE.2018.07.121.
[60] Zu S, Li W zhi, Zhang M, Li Z, Wang Z, Jameel H, et al. Pretreatment of corn stover [87] Venturin B, Frumi Camargo A, Scapini T, Mulinari J, Bonatto C, Bazoti S, et al.
for sugar production using dilute hydrochloric acid followed by lime. Bioresour Effect of pretreatments on corn stalk chemical properties for biogas production
Technol 2014;152:364–70. https://doi.org/10.1016/j.biortech.2013.11.034. purposes. Bioresour Technol 2018;266:116–24. https://doi.org/10.1016/j.
[61] Bustos G, Ramírez JA, Garrote G, Vázquez M. Modeling of the hydrolysis of sugar biortech.2018.06.069.
cane bagasse with hydrochloric acid. Appl Biochem Biotechnol - Part A Enzym Eng [88] UN Food and Agriculture Organisation R. FAOSTAT Statistics Data Base.
Biotechnol 2003;104:51–68. https://doi.org/10.1385/ABAB:104:1:51. FAOSTAT; 2016.
[62] Lai D, Deng L, Guo Q, Fu Y. Hydrolysis of biomass by magnetic solid acid †. Energy [89] Manzanares P, Ruiz E, Ballesteros M, Negro MJ, Gallego FJ, López-Linares JC, et al.
Environ Sci 2011;4:3552–7. https://doi.org/10.1039/c1ee01526e. Residual biomass potential in olive tree cultivation and olive oil industry in Spain:
[63] Gonzales RR, Sivagurunathan P, Kim SH. Effect of severity on dilute acid pre- valorization proposal in a biorefinery context. Span J Agric Res 2017;15:1–12.
treatment of lignocellulosic biomass and the following hydrogen fermentation. Int https://doi.org/10.5424/sjar/2017153-10868.
J Hydrog Energy 2016;41:21678–84. https://doi.org/10.1016/j.ijhydene.2016. [90] Romero-García JM, Niño L, Martínez-Patiño C, Álvarez C, Castro E, Negro MJ.
06.198. Biorefinery based on olive biomass. State of the art and future trends. Bioresour
[64] Jin Q, Zhang H, Yan L, Qu L, Huang H. Kinetic characterization for hemicellulose Technol 2014;159:421–32. https://doi.org/10.1016/j.biortech.2014.03.062.
hydrolysis of corn stover in a dilute acid cycle spray flow-through reactor at [91] Solarte-toro JC, Romero-garcía JM, López JC, Ruiz E, Castro E, Ariel C, et al.
moderate conditions. Biomass- Bioenergy 2011;35:4158–64. https://doi.org/10. Simulation approach through the biorefinery concept of the antioxidants, lignin
1016/j.biombioe.2011.06.050. and ethanol production using olive leaves as raw material. Chem Eng Trans
[65] Yu Z, Du Y, Shang X, Zheng Y, Zhou J. Enhancing fermentable sugar yield from 2018;70:925–30. https://doi.org/10.3303/CET1870155.
cassava residue using a two-step dilute ultra-low acid pretreatment process. Ind [92] Martínez-Patiño JC, Romero-García JM, Ruiz E, Oliva JM, Álvarez C, Romero I,
Crops Prod 2018;124:555–62. https://doi.org/10.1016/j.indcrop.2018.08.029. et al. High solids loading pretreatment of olive tree pruning with dilute phosphoric
[66] Kuglarz M, Alvarado-Morales M, Dąbkowska K, Angelidaki I. Integrated produc- acid for bioethanol production by Escherichia coli. Energy Fuels 2015;29:1735–42.
tion of cellulosic bioethanol and succinic acid from rapeseed straw after dilute-acid https://doi.org/10.1021/ef502541r.
pretreatment. Bioresour Technol 2018;265:191–9. https://doi.org/10.1016/j. [93] Cara C, Ruiz E, Ballesteros M, Manzanares P, Negro MJ, Castro E. Production of
biortech.2018.05.099. fuel ethanol from steam-explosion pretreated olive tree pruning. Fuel
[67] Dziekońska-Kubczak U, Berłowska J, Dziugan P, Patelski P, Pielech-Przybylska K, 2008;87:692–700. https://doi.org/10.1016/j.fuel.2007.05.008.
Balcerek M. Nitric Acid pretreatment of Jerusalem artichoke stalks for enzymatic [94] Cara C, Romero I, Oliva JM, Sáez F, Castro E. Liquid hot water pretreatment of
saccharification and bioethanol production. Energies 2018;11:2153. https://doi. olive tree pruning residues. Appl Biochem Biotechnol 2007;137–140:379–94.
org/10.3390/en11082153. https://doi.org/10.1007/s12010-007-9066-y.
[68] Sahu S, Pramanik K. Evaluation and optimization of organic acid pretreatment of [95] Requejo A, Peleteiro S, Rodríguez A, Garrote G, Parajó JC. Valorization of residual
cotton gin waste for enzymatic hydrolysis and bioethanol production. Appl woody biomass (Olea europaea trimmings) based on aqueous fractionation. J
Biochem Biotechnol 2018:1–14. https://doi.org/10.1007/s12010-018-2790-7. Chem Technol Biotechnol 2012;87:87–94. https://doi.org/10.1002/jctb.2687.
[69] Wang ZJ, Zhu JY, Zalesny RS, Chen KF. Ethanol production from poplar wood [96] Díaz MJ, Huijgen WJJ, Van Der Laan RR, Reith JH, Cara C, Castro E. Organosolv
through enzymatic saccharification and fermentation by dilute acid and SPORL pretreatment of olive tree biomass for fermentable sugars. Holzforschung
pretreatments. Fuel 2012;95:606–14. https://doi.org/10.1016/j.fuel.2011.12.032. 2011;65:177–83. https://doi.org/10.1515/HF.2011.030.
[70] Allen SG, Schulman D, Lichwa J, Antal MJ, Jennings E, Elander R. A comparison of [97] López-Linares JC, Romero I, Moya M, Cara C, Ruiz E, Castro E. Pretreatment of
aqueous and dilute-acid single-temperature pretreatment of yellow poplar saw- olive tree biomass with FeCl3prior enzymatic hydrolysis. Bioresour Technol
dust. Ind Eng Chem Res 2001;40:2352–61. https://doi.org/10.1021/ie000579. 2013;128:180–7. https://doi.org/10.1016/j.biortech.2012.10.076.
[71] Saeman JF. Hydrolysis of cellulose and decomposition of sugars in dilute acid at [98] Martín-Sampedro R, Fillat Ú, Ibarra D, Eugenio ME. Use of new endophytic fungi
high temperature. Ind Eng Chem 1945;37:43–52. https://doi.org/10.1021/ as pretreatment to enhance enzymatic saccharification of Eucalyptus globulus.
Ie50421a009. Bioresour Technol 2015;196:383–90. https://doi.org/10.1016/j.biortech.2015.07.
[72] Esteghlalian A, Hashimoto AG, Fenske JJ, Penner MH. Modeling and optimization 088.
of the dilute-sulfuric-acid pretreatment of corn stover, poplar and switchgrass. [99] Martínez-Patiño JC, Ruiz E, Romero I, Cara C, López-Linares JC, Castro E.
Bioresour Technol 1997;59:129–36. https://doi.org/10.1016/S0960-8524(97) Combined acid/alkaline-peroxide pretreatment of olive tree biomass for bioe-
81606-9. thanol production. Bioresour Technol 2017;239:326–35. https://doi.org/10.1016/
[73] Saeman JF. Kinetics of wood saccharification - hydrolysis of cellulose and de- j.biortech.2017.04.102.
composition of sugars in dilute acid at high temperature. Ind Eng Chem [100] Requejo a, Peleteiro S, Rodriguez a, Garrote G, Parajó JC. Second generation
1945;37:43–52. https://doi.org/10.1021/ie50421a009. bioethanol from residual woody biomass. Energy Fuels 2011;25:4803–10.
[74] Jensen J, Morinelly J, Aglan A, Mix A, Shonnard D. Kinetic characterization of [101] Solarte-toro JC, Romero-garcía JM, Susmozas A, Ruiz E. Techno-economic feasi-
biomass dilute sulfuric acid hydrolysis: mixtures of hardwoods, softwood and bility of bioethanol production via biorefinery of olive tree prunings (OTP): op-
switchgrass. Environ Energy Eng 2008;54:1637–45. https://doi.org/10.1002/aic. timization of the pretreatment stage. Holzforschung 2019;73:3–13. https://doi.
[75] Aguilar R, Ramı́rez J, Garrote G, Vázquez M. Kinetic study of the acid hydrolysis of org/10.1515/hf-2018-0096.
sugar cane bagasse. J Food Eng 2002;55:309–18. https://doi.org/10.1016/S0260- [102] Moncada J, Tamayo JA, Cardona CA. Integrating first, second, and third genera-
8774(02)00106-1. tion biorefineries: incorporating microalgae into the sugarcane biorefinery. Chem
[76] Zhang D, Ong YL, Li Z, Wu JC. Optimization of dilute acid-catalyzed hydrolysis of Eng Sci 2014;118:126–40. https://doi.org/10.1016/j.ces.2014.07.035.
oil palm empty fruit bunch for high yield production of xylose. Chem Eng J [103] Moncada BJ, Aristizábal MV, Cardona ACA. Design strategies for sustainable
2012;181–182:636–42. https://doi.org/10.1016/j.cej.2011.12.030. biorefineries. Biochem Eng J 2016;116:122–34. https://doi.org/10.1016/j.bej.
[77] Chen L, Zhang H, Li J, Lu M, Guo X, Han L. A novel diffusion-biphasic hydrolysis 2016.06.009.
coupled kinetic model for dilute sulfuric acid pretreatment of corn stover. [104] Rodrigues F, Pimentel FB, Oliveira MBPP. Olive by-products: challenge application
Bioresour Technol 2015;177:8–16. https://doi.org/10.1016/j.biortech.2014.11. in cosmetic industry. Ind Crops Prod 2015;70:116–24. https://doi.org/10.1016/j.
060. indcrop.2015.03.027.
[78] Kumar AK, Sharma S. Recent updates on different methods of pretreatment of [105] Roselló-Soto E, Koubaa M, Moubarik A, Lopes RP, Saraiva JA, Boussetta N, et al.
lignocellulosic feedstocks: a review. Bioresour Bioprocess 2017. https://doi.org/ Emerging opportunities for the effective valorization of wastes and by-products
10.1186/s40643-017-0137-9. generated during olive oil production process: non-conventional methods for the
[79] Behera S, Arora R, Nandhagopal N, Kumar S. Importance of chemical pretreatment recovery of high-added value compounds. Trends Food Sci Technol
for bioconversion of lignocellulosic biomass. Renew Sustain Energy Rev 2015;45:296–310. https://doi.org/10.1016/j.tifs.2015.07.003.
2014;36:91–106. https://doi.org/10.1016/j.rser.2014.04.047. [106] Talhaoui N, Taamalli A, Gómez-Caravaca AM, Fernández-Gutiérrez A, Segura-
[80] Taherdanak M, Zilouei H, Karimi K. The influence of dilute sulfuric acid Carretero A. Phenolic compounds in olive leaves: analytical determination, biotic

14
J.C. Solarte-Toro, et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

and abiotic influence, and health benefits. Food Res Int 2015;77:92–108. https:// cherd.2009.05.008.
doi.org/10.1016/j.foodres.2015.09.011. [110] Quintero JA, Cardona CA. Process simulation of fuel ethanol production from
[107] Paz Astudillo IC. Diseño Integral de Biorreactores Continuos de Tanque Agitado lignocellulosics using aspen plus. Ind Eng Chem Res 2011;50:6205–12. https://
Aplicados aProcesos de Fermentación. Manizales, Colombia: Universidad Nacional doi.org/10.1021/ie101767x.
de Colombia - Sede Manizales; 2010. ISBN (Hardcover) 9789587612554. [111] Wooley RJ, Putsche V. Development of an Aspen plus property database for bio-
[108] Humbird D, Davis R, Tao L, Kinchin C, Hsu D, Aden A, et al. Process design and fuels components. Golden, CO (United States): National Renewable Energy
economics for biochemical conversion of lignocellulosic biomass to ethanol. Laboratory; 1996:NREL/TP–425-20685https://doi.org/10.2172/257362.
Renew Energy 2011;303:147. https://doi.org/10.2172/1013269. [112] Al-Malah K. Aspen Plus: Chemical engineering applications. First edit. Wiley;
[109] Silva EAB, da, Zabkova M, Araújo JD, Cateto CA, Barreiro MF, Belgacem MN, et al. 2017.
An integrated process to produce vanillin and lignin-based polyurethanes from [113] Estadística INde. Encuesta Trimestral de Coste Laboral (ETCL) : Segundo trimestre
Kraft lignin. Chem Eng Res Des 2009;87:1276–92. https://doi.org/10.1016/j. de 2017; 2017.

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