Computers and Chemical Engineering 126 (2019) 35–53

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Computers and Chemical Engineering

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

An integral methodological approach for biorefineries design: Study

case of Colombian coffee cut-stems
Valentina Aristizábal-Marulanda a, Carlos Ariel Cardona Alzate a,∗, Mariano Martín b,∗
a
Instituto de Biotecnología y Agroindustria, Departamento de Ingeniería Química, Universidad Nacional de Colombia, Manizales campus, Km 07 vía al
Magdalena, Manizales, Colombia
b
Department of Chemical Engineering, Universidad de Salamanca, Pza. Caídos 1-5, 37008 Salamanca, Spain

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

Article history: This paper presents a generic and integral methodological approach for the design and assessment of
Received 29 July 2018 multiproduct biorefineries. The proposed methodology has been developed based on 2-stage strategy,
Revised 12 February 2019
conceptual design and optimization. In the conceptual design stage, the theoretical data about the biore-
Accepted 30 March 2019
finery are collected in order to build the superstructure. In the optimization stage, the formulated super-
Available online 6 April 2019
structure based on surrogate models, is optimized in order to generate the optimal biorefinery configu-
Keywords: ration where the utilities are produced internally from biomass via a cogeneration system. The proposed
Biorefinery framework is applied to evaluate the optimal exploitation of Coffee Cut-Stems (CCS). The results show
Design that ethanol is the most interesting product following dilute acid pretreatment and the fermentation of
Methodological approach C5 and C6 sugars due to the large yield of the process. However, an alternative scenario where energy is
Conceptual design and optimization the protagonist, results in the selection of power and heat as main products.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction framework for the preliminary assessment of chemical processes at

A biorefinery is defined as a system that involves assessing and
using a wide range of technologies to separate biomass into its
principal constituents (carbohydrates, protein, triglycerides, etc.),
which can be transformed in numerous products (fuels, chemicals,
power and heat, materials, and food and feed) (Moncada et al.,
2016). In the last years, these systems have attracted attention
in order to maximize the value of the products obtained from
biomass, to increase competitiveness and prosperity of bioindustry,
to reduce the dependency on fossil fuels by producing the same or
analogous substances demanded in the current market, to reduce
the emission of greenhouse gases and to stimulate regional and
rural development (Moncada et al., 2016). Currently, three differ-
ent approaches are used for the design and analysis of biorefiner-
ies: conceptual design, optimization and the early-stage method.
The conceptual design is based on hierarchy, sequencing and inte-
gration concepts (Douglas, 1988; Botero, 2012; Smith, 2005). The
optimization uses superstructure schemes and mathematical mod-
eling (Giarola et al., 2011; Sammons et al., 2007; Zondervan et al.,
2011). The early-stage method employs a multi-objective decision
∗ The methodology guarantees the selection of an optimal biore-
Corresponding authors.
E-mail addresses: ccardonaal@unal.edu.co (C.A. Cardona
mariano.m3@usal.es (M. Martín).
the laboratory stage (Moncada et al., 2015; Posada et al., 2013).
Conceptual design is the methodological approach where hi-
erarchy, sequencing and integration concepts are interlinked and
their combination carries to a process synthesis approach to obtain
theoretical and practical process models (Douglas, 1988; Smith,
2005). This approach has been applied to biorefinery level. For ex-
ample, Aristizábal et al. (2016); Cerón et al. (2015); Dávila et al.
(2017); Moncada et al. (2013) used this approach for the concep-
tual design of multiproduct biorefineries from first (i.e., sugarcane,
copoazu fruit and avocado), second (i.e., fresh fruit bunches) and
third (i.e., microalgae) generation. This methodology considers dif-
ferent scenarios, where technologies, feedstock distribution and in-
tegration levels (mass and energy), among others, are taken as
comparative parameters for the economic and environmental as-
sessment of the biorefineries.
On the other hand, many authors have applied the optimiza-
tion methodology to design of all types of biorefineries, such as,
(Bao et al., 2011; Bertran et al., 2017; Kelloway and Daoutidis, 2014;
Pham and El-Halwagi, 2011; Ponce-Ortega et al., 2012; Rosen-
gart, 2017; Zondervan et al., 2011). This approach considers a li-
brary of compact models for the generation of a superstructure of
transformation routes and products (i.e., a tree with all models).
Alzate), finery configuration assessing different optimization objectives as
maximizing yield and profit, minimizing costs, waste, fixed cost,

https://doi.org/10.1016/j.compchemeng.2019.03.038
0098-1354/© 2019 Elsevier Ltd. All rights reserved.
36 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53

point of view at early design stages. This methodology allows

Nomenclature to determine the processes sustainability and to diagnose their
strengths and weaknesses. Three sustainability indicators are con-
Variables sidered, (i) economic constrain (EC), (ii) energy related impact of
Z objective function (USD y−1 ) raw materials (EIRM) and (iii) process complexity (PC), which are
C cost consigned in a single index with the help of weighting factors to
f component flow have a fast comparison and to choose the better process (Moncada
S split of mass fraction (sugar) et al., 2015; Posada et al., 2013).
In this sense, this work proposes a general methodological ap-
Binary variables
proach for the design and analysis of biorefineries that promotes
y selection of process unit (binary)
the idea of using suitable tools and strategies to identify, select,
Subscripts and guarantee the existence of a promising biorefinery. The inte-
i component gral methodological approach has been developed based on a 2-
ligno components of lignocellulosic material stage strategy, conceptual design and optimization, focused on the
k unit generation of processing structures of biomass. Existing approaches
Rem remaining component develop similar methodological path in terms of theoretical foun-
r reaction dation, superstructure scheme, use of different technologies for the
n number of distribution stream same product and mathematical modeling (Bertran et al., 2017;
Moncada et al., 2016; Rosengart, 2017; Zondervan et al., 2011). De-
Superscripts spite these similarities, the proposed methodology is presented as
P product an evolution of existing approaches. The approach proposed in this
F feedstock work is based on 2-stage approach where the superstructure is
C chemicals put together using surrogate models for all of the stages based on
Reag reagent component rigorous simulation (Aspen Plus) and/or using experimental data
Ad added component versus typical short cut models. Furthermore, an integrated facility
Util utility is considered that provides the utilities required for it to be self-
ww wastewater management sustainable, a consideration that results in the partial consumption
Inv inversion of raw material that has not previously considered in the litera-
IN unit inlet ture. So far, C5 andC6 sugars were no distinguished as resource
OUT unit outlet for different chemicals. This feature is added to the superstructure
S substrate due to the additional possibilities that can provide to the biorefin-
Liq1 liquid in filter 1 ery. Finally, wastewater treatment is also integrated. This approach
Sol1 solid in filter 1 is used in an example of strategic importance for Colombia, the
R outlet of reaction evaluation of the use of the residues from the coffee production
Liq2 liquid in filter 2 industry. However, the methodology presented is general and can
Sol2 solid in filter 2 be used for any other case.
w waste This work is organized as follows: Section 2 indicates a de-
Liq3 liquid in filter 3 tailed explanation about the general methodological approach for
Sol3 solid in filter 3 the design and analysis of biorefineries. Afterwards, in Section 3,
n reaction number a study case is presented and solved using the proposed method-
Parameters ology and well-known computational tools (i.e., GAMS and Aspen
φ mass fraction of feedstock Plus). Subsequently, the results obtained are explained and dis-
Pr sale price cussed in Section 4. Finally, conclusions and future research works
β utility consumption respect to feedstock flow in the are highlighted in Section 5.
processing stage
μ proportion of added component respect to feedstock 2. Integral methodological approach
α yield
x fraction A general methodological approach is proposed that fuses two
MW molar weight well-known methodologies, conceptual design and optimization,
θ conversion which are articulated through the formulation of a superstructure
γ stoichiometric coefficient problem (Martín and Grossmann, 2012; Moncada et al., 2016). A
δ proportion of added component respect to reference superstructure of alternatives combines continuous (e.g., operating
compound conditions) and discrete variables (e.g., feedstock distribution). Ac-
σ fraction separated of product 1 cording to the decision-making nature of the problem, its approach
ϱ fraction separated of product 2 and solution is based on a problem of Mixed-Integer Nonlinear
M large number of big-M Programming (MINLP). This problem is solved in order to generate
the optimal biorefinery topology.
The superstructure formulation depends on biorefinery goals.
environmental impact, etc. This methodology has the limitation Likewise, the problem formulation requires large amounts of data
that does not allow the selection of various conversion routes taken from various resources, development and assessment of all
that are simultaneously attractive from two or more perspectives alternatives, mathematical model-building of alternatives and so-
(Ponce-Ortega et al., 2012). lution of the mathematical programming problem (Bertran et al.,
Moncada et al. (2015); Patel et al. (2012); Posada et al. 2017). All steps mentioned before are required for each con-
(2013) proposed the use of early-stage method for the biorefineries stituent unit of system that is assessed. Fig. 1 indicates in detail
design, which aims to assess systematically the biorefinery prod- the steps that compose the proposed methodological approach for
ucts to identify those with the best potential from a sustainability biorefineries design. The methodology does not consider loops or
 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53
Fig. 1. Generic methodology for the biorefineries design.
feedbacks because in the first steps, the user can involve an unde-
fined number of feedstocks, technologies and products. These as-
pects generate uncertainty, which is translated in the possibility of
to have a feedback. However, if the conceptual design stage is ap-
propriately carried out, the uncertainty disappears and many pos-
sibilities of biorefinery can be assessed to generated one or two
optimal and integrated biorefinery configurations.
2.1. Stage 1: Conceptual design
The objective of the conceptual design consists of searching
concepts or principles for theoretically structuring the problem. In
this point, the identified problem is analyzed and one or more
solutions are synthesized and evaluated with respect to imposed
constraints. This stage demands high levels of knowledge and inno-
vation, characterized by the dynamic evolution. A comprehensive
and detailed description of each step for the proposed methodolog-
ical approach is presented below.
• Step 1: Define the general objective, feedstock(s) and set of
products
The application of the proposed methodology to a study case
is supported in its general objective. The nature of the objective
depends on the problem that is solved. Examples of general ob-
jectives for which it is applicable this methodology are, the selec-
tion of a better configuration of a determined system or processing
routes for one or more products or to choose a feedstock between
a set of feedstocks. In this step, one or a set of feedstocks and
a set of products are defined. Availability, price, logistics, location
and chemical composition are decisive parameters when defining
a feedstock. Market demand and feedstock potential allows identi-
fying interesting products.
37
• Step 2: Apply know-how experience, hierarchical decomposi-
tion and sequencing concepts
This step seeks to structure the biorefinery in a logical and in-
terconnected way based on knowledge and experience. This step
is used for the selection of technologies through a hierarchical
decomposition concept, which corresponds to the onion diagram
where the reaction stage is the fundamental part in the process
or system (Sánchez Toro, 2008). This heuristic concept is empha-
sized in a decomposition strategy and alternatives trace, which al-
lows the "quick" location of technological configurations close to
optimal solutions (Sánchez Toro, 2008). In addition, the nature of
this approach allows the definition of the process diagram in a se-
quential and evolutionary way and discards configurations that do
not lead to "good" designs, reducing the number of alternatives
(Sánchez Toro, 2008). In this step, a set of technologies are de-
fined that are used in the superstructure. The maturity level and
information about the available technologies contribute to define
promising and critical processing routes.
• Step 3: Collect experimental results, data from literature,
databases and bibliography
Feedstock characterization, yields, conversions, operating condi-
tions, process configuration, costs of feedstock, reagents and prod-
ucts are data acquired from bibliographic resources, academic or
industrial partners and databases. If some information is not avail-
able, it must be estimated (e.g., equipment cost) on experimentally
procedure.
2.2. Stage 2: Optimization
The optimization stage has as objective to decide on the topol-
ogy of the biorefinery by solving the superstructure problem
through mathematical programming.
• Step 4: Propose a superstructure
The theoretical concepts mentioned in the conceptual design
stage allow to build a tree-branching (i.e., a superstructure) of al-
ternative processing routes to transform a feedstock into a set
of products, namely, a superstructure that represents a decision-
making problem (Bertran et al., 2017; Rosengart, 2017). Boxes
(units) denote the process alternatives, while arrows are used to
connect the viable interactions between boxes. The units are used
to represent a process technology composed by one or more units.
The superstructure components are arranged with respect to pro-
cessing stages considered in a biorefinery, pretreatment, reaction
and/or separation stages.
At this point, many biorefinery combinations are considered ac-
cording to aspects such as, supply chain, alternative technologies at
each stage and feedstock distribution, among others. These consid-
erations must be taken into account for the formulation or solution
of the problem.
• Step 5: Developing of the surrogate models
The suitable connection and interaction between collected data
in Step 3, allows the generation of mass and energy balances of
process units that constitute the system. The modeling of process
units is carried out according to the problem nature.
Pretreatment, reaction and separation stages of superstructure
are modeled using a generic set of equations, through a sequence
of process operations (i.e., mixing, milling, cooling/heating, main
reaction, filtration, second reaction, separation). The unit allows
several inlets and outlets, focusing on the consideration of utili-
ties, reagents and/or solvents streams. A general scheme and de-
tailed scheme of inputs and outputs in a process unit are shown in
Fig. 2A and B, respectively.
38 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53
Fig. 2. (A) General process unit scheme. (B) Extended unit scheme applied to pretreatment, reaction and separation stages.
The seven process operations that can be considered in a pro-
cess unit are described in detail below in order to understand the
role that every one of them plays.
Mixing: It is used to mix flows from different streams or to in-
clude components in the main flow such as, reagents and/or added
components (i.e., solvents). If a new component wants to be in-
cluded, its flow should be determined based on the mass flow of
a reference component in the main stream (e.g., kg added com-
ponent per kg feedstock) with a parameter called “proportion of
added component respect to feedstock” (represented by μ).
Milling: this operation represents the particle size reduction of
the feedstock.
Heat exchanger: It represents the temperature conditioning in
the inlet streams to main reactor.
Main reactor: in this process operation, a chemical transforma-
tion is carried out (e.g., alkaline hydrolysis, enzymatic hydrolysis
and fermentation, among others). The model requires data about
yields or stoichiometric reaction(s) with the respective stoichio-
metric coefficients of all involved components as well as conver-
sion(s) of limiting reagent.
Filter: this process operation represents the separation of a solid
from liquid stream with a split parameter called fraction (repre-
sented by xLiq ).
By-products reactor: in this process operation, a secondary
chemical reaction such as, detoxification (described by a stoichio-
metric reaction) is carried out. It requires information about stoi-
chiometric coefficients of reagents and products, and conversion.
Separator: this process operation represents downstream pro-
cesses such as, distillation, evaporation, crystallization and spray
dry, among others. The separation processes can be coupled in se-
quential way (e.g., distillation columns train or crystallization fol-
lowed by spray dry). Recovery percentage of main component is
the most important data to model in this process operation. From
these downstream processes two outlet streams are obtained, the
first one includes the interest component and the second one con-
tains the remaining components or wastewater.
 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53
Simultaneously to the generation of optimal biorefinery config-
uration, energy requirements are quantified in terms of electricity,
low pressure steam (LPS), medium pressure steam (MPS) and high
pressure steam (HPS). Once these are quantified, a cogeneration
system is coupled to the biorefinery in order to generate a quantity
equal or greater than energy requirements. The addition of cogen-
eration system to the optimal biorefinery configuration promotes
to the generation of optimal and integrated biorefinery configura-
tion.
In addition, the objective function should be defined. The ob-
jective function evaluates the system performance based on one or
more criteria (technical, economic, environmental, among others).
The selection of the criteria depends on the optimization objec-
tives (i.e., maximize yield, minimize cost, minimize environmen-
tal impact, etc.). In the case of the model of the case study, see
Appendix A, the objective function considers the annual earnings
from sales of products and annual expenses related to operat-
ing costs (utilities, reagents and solvents), wastewater management
cost and capital investment.
• Step 6: Solving the optimization problem
Due to the fact that the superstructure is a decision-making
problem, it imitates the approach of a Mixed-Integer Nonlinear
Program (MINLP). Although in some situations, it can be reduced
to a Mixed-Integer Linear Program (MILP or MIP) using linear mod-
els and/or approximations. As result of the solution of optimization
problem, an optimal topology for biorefinery configuration is gen-
erated. The mathematical solution for the superstructure problem
is linked to the problem nature.
3. Study case: coffee cut-stems (CCS) biorefinery
Each step contemplated in the theoretical description of pro-
posed methodology is applied to the study case of a multiprod-
uct biorefinery from CCS, as is indicated below. Previous work
from the group (Triana et al., 2011) shows that CCS are a promis-
ing raw material for the production of bioproducts in tropical cli-
mates because of the wide availability and high yield per hectare.
When there is renovation of coffee plantations by "zoqueo" a
high availability of wood is presented, which is called Coffee Cut-
Stems (CCS) and normally are used as potential energy source
(Valencia, 20 0 0). The renovation process is carried out in order
to maintain a good and constant production of coffee and in-
volves cutting the main coffee stem at a height between 20 and
30 cm above the ground (García Velásquez, 2016). CCS biorefin-
ery is located in Department of Caldas (central zone of Colom-
bia) because this zone is one of the largest coffee producers in
Colombia. To determine the CCS availability in Caldas the follow-
ing assumptions are considered: (i) the coffee tree produces as
fruit the cherry coffee and it is used as feedstock in coffee process-
ing. (ii) The “pergamino” coffee is the product obtained at the end
of the coffee processing. (iii) The Centro Nacional de Investigación
de Café (CENICAFÉ) determined that 4.915 kg of cherry coffee are
required to produce 1 kg of "pergamino" coffee (Montilla et al.,
2008). (iv) According to CENICAFÉ, 0.6 kg of CCS are obtained per
kg of processed cherry coffee and (v) every 5 years, CCS is har-
vested (Rodríguez and Franco, 2010).
In this sense, Caldas had a coffee production of 62,869 ton
in 2014 (Agronet, 2017), corresponding to 309,0 0 0 ton of coffee
cherry. These values allow determining the productivity of CCS
per year, which is 37,080 ton, thus, a processing plant capacity of
1.176 kg s-1 of feedstock. The CCS biorefinery considers an annual
productivity of 8016 h corresponding to 24 h a day and 334 days
a year. CCS present a chemical composition of cellulose, hemicel-
lulose, lignin, extractives and ash corresponding to 40.39, 34.01,
39
10.13, 14.18 and 1.27% (w/w dry basis), respectively. The moisture
content is 8.7% (w/w) (García et al., 2017a).
3.1. Stage 1: Conceptual design
• Step 1: Define the general objective, feedstock(s) and set of
products
The study case has as goal to determine the most convenient
products from an economic perspective in a CCS biorefinery con-
sidering different technologies, feedstock distribution and sugars
use. CCS biorefinery considers one feedstock (coffee cut-stems) and
seven products of different nature, biofuels (ethanol and butanol),
biochemicals (xylitol, furfural and lactic acid), biomaterials (poly-
hydroxybutyrate - PHB) and energy (electricity). These products
are selected in order to combine product-driven biorefinery and
energy-driven biorefinery, giving versatility to proposed biorefinery
and secure self-supply of required energy (IEA Bioenergy Task42,
2014).
• Step 2: Apply know-how experience, hierarchical decomposi-
tion and sequencing concepts
CCS biorefinery is composed by three processing stages, pre-
treatment, reaction and separation. Additionally, a cogeneration
system (it is explained in Step 5), which supplies the biorefinery
energy requirements, (i.e., electricity and steam) and a wastewater
treatment system are considered.
Two types of particle size reduction technologies are taken into
account. The first one has the function to condition the CCS that
enter to the pretreatment stage and the second one aims to condi-
tion the CCS that go to cogeneration system. These units are syn-
ergistically connected in order to make the correct feedstock dis-
tribution that allows obtaining at least one product adapted with
a cogeneration system.
The biorefinery considers three platforms (glucose, xylose and
syngas), which have the function to articulate the pretreatment
stage with reaction and separation stages. Xylose flow can be used
for the production of xylitol and/or furfural. Meanwhile, glucose
flow can be distributed for the production of ethanol, PHB, butanol
and/or lactic acid. An option is to mix xylose and glucose flows to
produce ethanol. All these alternatives are possible solutions of the
proposed biorefinery. The syngas platform is only used to produce
heat and power.
In the next step, the methodological details that are used in the
formulation and building of the CCS biorefinery are indicated.
• Step 3: Collect experimental results, data from literature and
databases
The pretreatment stage considers six different technologies:
particle size reduction, dilute-acid hydrolysis, alkaline hydrolysis,
organosolv, liquid hot water (LHW) and ammonia fiber explosion
(AFEX). Table 1 indicates the operating conditions for each tech-
nology used in this stage.
In the reaction stage, furfural, ethanol and butanol can be pro-
duced through two process alternatives each. In the furfural pro-
duction, dehydration reaction using HCl and H2 SO4 as different
catalysts are considered. Fermentation processes using Zymomonas
mobilis and Saccharomyces cerevisiae as microorganisms are taken
into account for ethanol production. In the butanol production,
fermentation processes using Clostridium beijerinckii and Clostrid-
ium acetobutylicum as microorganisms are considered. The produc-
tion of xylitol, PHB and lactic acid only considers one technology.
Fermentation processes using Candida guilliermondii, Bacillus mega-
terium and Escherichia coli as microorganisms are considered for
xylitol, PHB and lactic acid obtaining, respectively. To reduce the
40 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53

Table 1
Information about process units of pretreatment stage considered in CCS-superstructure.

Technology Operating conditions References

Particle size reduction I
Particle size reduction
II
Dilute-acid hydrolysis
and detoxification
Alkaline hydrolysis and
detoxification
Organosolv
Liquid hot water
Ammonia fiber
explosion
0.4 mm, content moisture <10% and specific energy (kWh/kg) 0.03 (García Velásquez, 2016;
Tumuluru et al., 2014)
10 mm, content moisture <10% and Specific energy (kWh/kg) 0.00391 (Di Fulvio et al., 2015; García
Velásquez, 2016; Vidal and
Martín, 2015)
Dilute-acid hydrolysis (Aristizábal Marulanda, 2015;
García Velásquez, 2016)
2% (v/v) H2 SO4 , 110 °C, 5 h, 1:10 (Solid to liquid ratio)
Detoxification
60 °C, 20 min, pHfinal 6.5
Glucose yield: 0.0574 g glucose/g substrate
Xylose yield: 0.2208 g xylose/g substrate
C a(OH )2 + H2 SO4 → C aSO4 + 2H2 O
Utilities
CW: 120.77 kg/kg CCS, LPS: 0.43 kg/kg CCS
Alkaline hydrolysis (Oka et al., 2013)
KOH 1 N, 150 °C, 1 h, 1:25 (Solid to liquid ratio)
Glucose yield: 0.0649 g glucose/g substrate
Xylose yield: 0.2667 g xylose/g substrate
Detoxification
30 °C, 10min
3KOH + H3 P O4 → K3 P O4 + 3H2 O
Utilities
CW: 100.44 kg/kg CCS, LPS: 0.26 kg/kg CCS, MPS: 0.48 kg/kg CCS
50%(v/v) ethanol, 180 °C, 4 MPa, 1 h, 1:10 (Solid to liquid ratio) (Pan et al., 2006)
1.25%(w/w dried wood) H2 SO4
Glucose yield: 0.0055 g glucose/g substrate
Xylose yield: 0.0937 g xylose/g substrate
Utilities
HPS: 3.25 kg/kg CCS
5%(w/v) substrate in water, 180 °C, 4 MPa, 20 min, 500rpm (Yu et al., 2010)
Glucose yield: 0.02 g glucose/g substrate
Xylose yield: 0.825 g xylose/g substrate
Utilities
HPS: 3.23 kg/kg CCS
180 °C, 700 psi, 4.82 MPa, 30 min, (Balan et al., 2009)
2:1 (ammonia to biomass ratio), 233% moisture (dry biomass basis)
Glucose yield: 0,0 0 019 g glucose/g substrate
Xylose yield: 0,0 0 021 g xylose/g substrate
Utilities
HPS: 2.10 kg/kg CCS

CW, cooling water.

boundaries of this work, the solids that did not react in the en-
zymatic hydrolysis unit are not used as an option for electricity
generation due to the high levels of energy consumed in the dry-
ing process in order to remove its moisture content. Table 2 indi-
cates the operating conditions for process units used in the reac-
tion stage.
In the separation stage, furfural, ethanol and butanol are pu-
rified by distillation, xylitol through crystallization, PHB by spray
dryer and lactic acid using salts precipitation. Table 3 shows the
description of process units considered in the separation stage in-
cluding the wastewater treatment unit. Aspen Plus v9.0 is used as
tool to generate the mass and energy balances. The information
consigned in Tables 1, 2 and 3 is fed to the simulator. Each process
unit is simulated individually.
3.2. Stage 2: Optimization
• Step 4: Propose a superstructure
For the CCS biorefinery case of study, the formulated super-
structure is shown in Fig. 3, which includes 27 process units dis-
tributed in three stages: pretreatment, reaction and separation, and
a cogeneration system. Two types of particle size reduction are
considered before pretreatment stage; due to the cogeneration sys-
tem requires a feedstock size different to the pretreatments (see
Table 1). In the biorefinery superstructure, each process alternative
corresponds to one process unit.
• Step 5: Developing of the surrogate model
Data reported in Tables 1, 2 and 3 are the base to generate mass
and energy balances for each process unit. The calculation of the
mass balance for unit of dehydration using HCl as catalyst for the
furfural production is presented as an example in the Supplemen-
tary material. In this process unit, two types of chemical reactions
are carried out: dehydration reaction (main) and neutralization re-
action (secondary). The calculation of mass balances for each pro-
cess unit is made in a similar way. The optimization problem of
superstructure is raised as indicates the generic model shown in
the Appendix A.
The proposed cogeneration system aims to supply the energy
requirements of optimal biorefinery configuration, considering the
generation of electrical and thermal energy. The technology used in
cogeneration system is known as Biomass Integrated Gasification
Combined Cycle (BIGCC) (Balat et al., 2009; Rincón et al., 2014),
which is composed mainly by three stages, gasification, gas tur-
 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53
Table 2
Information about process units of reaction stage considered in CCS-superstructure.
Technology
Enzymatic hydrolysis
Fermentation Candida guilliermondii
Dehydration with HCl
Dehydration with H2 SO4
Fermentation Zymomonas mobilis
Fermentation Saccharomyces cerevisiae
Fermentation Bacillus megaterium
41
Operating conditions References
50 °C, 48 h, 1:10 (Solid to liquid ratio), Celluclast 1.5 L and Viscozyme L in buffer (Aristizábal Maru-
solution of Sodium Citrate 0.05 M (pH 4.8–5.0) landa, 2015)
Glucose yield: 0.1198 g glucose/g substrate
Xylose yield: 0.0133 g xylose/g substrate
Utilities
LPS: 11.58 kg/kg xylose and glucose
30 °C, 200 rpm, 48 h (Hernández-Pérez et al.,
2016)
Xylitol yield: 0.47 g xylitol/g sugars
79.2% xylose consumption
3C5 H10 O5 → 5C2 H6 O + 5C O2
Utilities
CW:1702.65 kg/kg xylitol
180 °C, 11 bar (Martín and
Grossmann, 2016)
CrCl3 catalyst is a molar ratio of 0.06 with the sugars, NaCl added to saturate the
water (35 g of NaCl per 100 g of H2 O), HCl is 0.12 mol/L and butanol is twice the
aqueous phase
Conversion glucose to HMF 67.5%
Conversion xylose to furfural to 56%
Selectivity to glucose 0.85
Selectivity to xylose 0.8
C6 H12 O6 → C6 H6 O3 + 3H2 O
C5 H10 O5 → C5 H4 O2 + 3H2 O
Neutralization
80 °C, 10min
NaOH + HCl → NaCl + H2 O
Utilities
HPS: 93.99 kg/kg furfural and HMF
NaCl corresponds to that needed to saturate the water (35 g of NaCl per 100 g of H2 O) (Martín and Grossmann,
and butanol 2016; Moncada et al.,
2016b)
is twice the aqueous phase
150 °C, 1 bar, 4 h, 8 g/L H2 SO4 as catalyst
Furfural yield: 0.91 g furfural/g xylose
C5 H10 O5 → C5 H4 O2 + 3H2 O
Neutralization
60 °C, 20min
C a (OH )2 + H2 SO4 → C aSO4 + 2H2 O
Utilities
MPS: 25.23 kg/kg furfural
33 °C, 80 h (Quintero Suárez, 2011)
(Mariscal Moreno, 2011)
Conversion reducing sugars to ethanol 74.43% (the same for both)
C6 H12 O6 → 2C2 H6 O + 2C O2
3C5 H10 O5 → 5C2 H6 O + 5C O2
In this process unit, glucose and xylose are assumed as unique reducing sugars.
Nutrients (g/100 kg sugars)
Na3 PO4 .12H2 O: 101.2
Urea: 212.2
FeCl3 .H2 O: 1.1
MgSO4 .7H2 O: 1.1
Utilities
CW: 1521.47 kg/ethanol
32 °C, 72 h, 170rpm (Moncada et al., 2016b)
Conversion glucose to ethanol 91.3%
C6 H12 O6 → 2C2 H6 O + 2C O2
(Mariscal Moreno, 2011)
Nutrients (g/100 kg sugars)
Na3 PO4 .12H2 O: 101.2
Urea: 212.2
FeCl3 .H2 O: 1.1
MgSO4 .7H2 O: 1.1
Utilities
CW: 1994.86 kg/kg ethanol
33 °C, 250 rpm, 42 h (Naranjo Vasco, 2014)
Air 12 L/min
0.4 g PHB/g glucose consumed
57.5% glucose consumed
C6 H12 O6 + 0.99O2 + 0.38N H4 N O3 → 4C H1.74 O0.96 N0.19 + 3.28H2 O + 2C O2
Utilities
CW: 3536.17 kg/kg PHB
(continued on next page)
42 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53

Table 2 (continued)

Fermentation Clostridium beijerinckii 34 °C, 72 h (Malmierca et al., 2017;

Qureshi and Blaschek,
1999)
100% sugars are transformed mainly into butanol and acetone
100C6 H12 O6 →
82.68C4 H10 O + 23.15C3 H6 O + 2.03C2 H6 O + 195.7C O2 + 10.44H2 + 100.6H2 O
Pervaporation
Heated up to 70 °C and cool down to 34 °C before recycling the retentate to the
fermenter. Butanol yield in permeate side is 98.67%
Utilities
CW: 3391.93 kg/kg AB
LPS: 11.68 kg/kg AB
Refrigerant: 3848.94 kg/kg AB
Fermentation Clostridium 37 °C, 72 h (Ramirez, 2018)
acetobutylicum
Conversion glucose to butanol 45.27%
Conversion glucose to ethanol 3.94%
Conversion glucose to acetone 18.45%
C6 H12 O6 + H2 O → C3 H6 O + 3C O2 + 4H2
C6 H12 O6 → C4 H10 O + 2C O2 + H2 O
C6 H12 O6 → 2C2 H6 O + 2C O2
Utilities
CW: 4866.37 kg/kg ABE
LPS: 18.50 kg/kg ABE
Refrigerant: 6064.77 kg/kg ABE
Fermentation Escherichia coli 37 °C, 48 h (Ramirez, 2018)
Conversion xylose to lactic acid 72.69%
Total conversion of glucose
C6 H12 O6 → 2C3 H6 O3
3C5 H10 O5 → 5C3 H6 O3
Utilities
CW: 680.91 kg/kg LA

CW, cooling water.

Fig. 3. Graphical scheme of formulated superstructure for CCS biorefinery.

bine and Heat Steam Recovery Generator (HRSG). Fig. 4 indicates
the detailed flowsheet of cogeneration system. The operating con-
ditions, specifications and reactions of each stage are shown in
Table 4.
The gasification stage contains three reaction zones such as, py-
rolysis, oxidation and reduction (García et al., 2017a; García et al.,
2017b; Sharma, 2011). Syngas is the main product from biomass
gasification, which it is a mixture of gaseous compounds as car-
bon monoxide (CO), carbon dioxide (CO2 ), water (H2 O), hydrogen
(H2 ), methane (CH4 ) and small amounts of ashes. In pyrolysis zone,
biomass undergoes into the devolatilization, where it is decom-
posed into carbon (assumed as char), CO, CO2 , H2, H2 O, light hy-
drocarbons (assumed as CH4 ) and heavy hydrocarbons (assumed
as benzene - C6 H6 ). Then, in the oxidation zone all the compo-
nents from pyrolysis react with oxygen to produce CO2 , CO and
H2 O. Finally, the produced char in pyrolysis zone passes to the re-
duction zone, where char gasification takes place to produce CO,
H2 and CH4 . A cleaning system composed by a cyclone and a filter
 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53
Table 3
Information about process units of separation stage considered in CCS-superstructure.
Technology
Xylitol crystallization
Furfural purification I
Furfural purification II
Ethanol purification I and II
PHB purification
43
Operating conditions References
Concentration of xylitol in broth 16 g/L (De Faveri et al., 2002;
Garcia et al., 2013;
Hernández et al., 2016)
Evaporation
50 °C and 0.16 bar
Concentration of xylitol until 600 g/L
Crystallization
−5 °C, commercial xylitol added 1 g/L to favor the nucleation of xylitol crystals. Crystallization
yield 0.56 and pure degree 1
Recovery 56% of xylitol
Utilities
LPS: 135.64 kg/kg xylitol
Refrigerant: 99.36 kg/kg xylitol
Separator (aqueous and organic phase) and two stripping columns. Organic phase is distillated. (Martín and
Grossmann, 2016; De
Rodrigues and
Guirardello, 2012)
Respect to inlet stream to separator, the aqueous phase contains, water ≤94%, butanol ≤1%,
50% of remaining sugars and 100% of NaCl.
Column 1
Reflux ratio at 1.95, 29 stages, feed stage 23, 0.5 bar
Column 2
Reflux ratio at 0.55, 62 stages, feed stage 27, 0.5 bar
Recovery 99.9% of 1-butanol
Recovery 87% of furfural + HMF (94% w/w of purity)
Utilities
LPS:353.61 kg/kg furfural and HMF
MPS: 561.65 kg/kg furfural and HMF
Separator (aqueous and organic phase) and two stripping columns. Organic phase is distillated. (Martín and
Grossmann, 2016; De
Rodrigues and
Guirardello, 2012)
Respect to inlet stream to separator, the aqueous phase contains, water ≤94%, butanol ≤1%,
50% of remaining sugars and 100% of NaCl.
Column 1
Reflux ratio at 2, 55 stages, feed stage 22, 0.5 bar
Column 2
Reflux ratio at 0.45, 72 stages, feed stage 39, 0.5 bar
Recovery 99.9% of 1-butanol
Recovery 85% of furfural (96% w/w of purity)
Utilities
LPS: 239.47 kg/kg furfural
MPS: 380.57 kg/kg furfural
The concentration of ethanol in water is 5%–6% using Z. mobilis. (García et al., 2017;
Moncada et al., 2016)
The concentration of ethanol in the water is 6%–8% using S. cerevisiae
Column 1 and 2
Reflux ratio at 1.5, 12 stages, feed stage 6, 0.5 bar.
In column 1, the ethanol is concentrated up to 45%–50% w/w and in the second column, the
ethanol is concentrated until the azeotropic point (96% w/w).
Molecular sieves
Recovery 99.8% of ethanol (99.6% w/w of purity).
Utilities I
CW: 600.3 kg/kg ethanol
LPS: 7.27 kg/kg ethanol
Utilities II
CW: 570.41 kg/kg ethanol
LPS: 7.06 kg/kg ethanol
The fermentation broth with a PHB and cells concentration of 4.2 and 7.1 g/L, respectively. (Naranjo Vasco, 2014;
Posada et al., 2011)
Digestion and filtration
1:2 NaOCl/cell mass ratio. Enzyme concentration: 2 wt%
Washing
H2 O2 -water washing concentration: 1.2 v/v%.
H2 O2 -water washing: mixture ratio 1:1.
Evaporation
90 °C, 0.5 bar and 20.2% w/w PHB purity
Spray dryer
Recovery 99.9% of PHB (99.6% w/w of purity).
Utilities
CW: 8.05 kg/kg PHB
LPS: 556.88 kg/kg PHB
(continued on next page)
44 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53

Table 3 (continued)

Acetone and Butanol purification Heat exchanger 1 (Malmierca et al., 2017)

50 °C and 1 bar
Column 1
Reflux ratio at 1.5, 6 stages, feed stage 4, 1 bar
Recovery 95.7% of water in the bottoms (99% w/w of purity).
Heat exchanger 2
62 °C and 0.5 bar
Column 2
Reflux ratio at 2.2, 15 stages, feed stage 5, 0.5 bar
Recovery 95.6% of acetone in the top (99% w/w of purity).
Heat exchanger 3
91.78 °C and 1 bar
Column 3
Reflux ratio at 2, 26 stages, feed stage 22, 1 bar
Recovery 70.8% of butanol in the bottoms (99% w/w of purity).
Utilities
LPS: 44.09 kg/kg AB
Acetone, Butanol and Ethanol purification The fermentation broth with butanol concentration of 8.65 g/L (Malmierca et al., 2017;
Xie et al., 2015)
Heat exchanger 1
50 °C and 1 bar
Column 1
Reflux ratio at 1.5, 6 stages, feed stage 4, 1 bar
Recovery 95.5% of water in the bottoms (99% w/w of purity).
Heat exchanger 2
62 °C and 0.5 bar
Column 2
Reflux ratio at 2.2, 15 stages, feed stage 5, 0.5 bar
Recovery 96.9% of acetone in the top (99% w/w of purity).
Column 3
Reflux ratio at 1.5, 12 stages, feed stage 6, 0.5 bar
Recovery 90% of ethanol in the top (96% w/w of purity).
Heat exchanger 3
91.78 °C and 1 bar
Column 4
Reflux ratio at 2, 26 stages, feed stage 22, 1 bar
Recovery 87.9% of butanol in the bottoms (99% w/w of purity).
Utilities
LPS: 51.31 kg/kg ABE
Lactic Acid purification Precipitation reaction (Garcia et al., 2013;
Komesu et al., 2017;
Nakano et al., 2012)
Ca(OH)2 added in aqueous solution (Lime: water ratio 15:85 w/w), 95 °C
2C3 H6 O3 + C a (OH )2 → C a (C3 H5 O3 )2 + 2H2 O
Washer
Solid content less than 1% w/w in the liquid fraction
Acidification reaction
H2 SO4 added in aqueous solution (H2 SO4 :water ratio 15:85 w/w), 20 °C
C a(C3 H5 O3 )2 + H2 SO4 → 2C3 H6 O3 + C aSO4
Evaporation
40 °C and 0.04 bar
Recovery 98.8% of lactic acid (80% w/w of purity – food grade).
Utilities
CW: 36.11 kg/kg LA
Refrigerant: 28.15 kg/kg LA

CW, cooling water.

is used to separate the remaining char, ashes and impurities from
produced syngas.
The gas turbine uses the syngas to produce power and flue
gases. The intercooled, reheat and regenerative (ICRHR) cycle is
composed of two compressors, one combustor and two turbines
(Razak, 2007). This type of turbines present high thermal efficiency
and the ICRHR cycle decreases the heat input requirements to the
system. The turbine uses atmospheric air at 14.85 °C and 1 bar.
Both compressors operate at the same pressure ratio in order to
minimize their work inputs. In the same way, both turbines op-
erate at the same pressure ratio to maximize their work outputs
(Razak, 2007). The syngas combustion is carried out in a rich-air
atmosphere to achieve a complete combustion.
The outlet gases from the gas turbine are mixed and com-
busted with more syngas in order to increase the temperature. The
hot gases obtained are brought to three steam generators to pro-
duce steam of different qualities, where each one is composed by
three heat exchangers (HX) with defined functions. The first HX
increases the water temperature until its saturation point, the sec-
ond one provides heat to convert the saturated liquid into satu-
rated steam and the third one increases the steam temperature
over its saturation point. The mentioned description corresponds
to a HRSG.
• Step 6: Solving the optimization problem
The generic model is formulated as a nonlinear program-
ing problem, namely MINLP, which follows the structure pre-
sented in Appendix B. This uses DICOPT as solver, which is based
on three key ideas as, Outer Approximation, Equality Relaxation
and Augmented Penalty (“GAMS. Solver manuals,” 2018). GAMS
 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53
Fig. 4. Flowsheet of cogeneration system.
(General Algebraic Modeling System) is used as computer tool
to solve the optimization problem, which combines mathematical
language with conventional programming concepts.
3.3. Economic aspects
The investment costs are calculated using the software Aspen
Process Economic Analyzer v9 (Aspen Technologies, Inc., USA). The
reference year for the estimation of investment costs is 2015. This
analysis is estimated in US dollars for a 10-year period at an an-
nual interest rate of 20% and working capital of 5% (typical for the
USA economy). Table 5 summarizes the economic data for raw ma-
terial, reagents, solvents, products and utilities. In the supplemen-
tary material file, the design specifications of all equipments used
in this work are presented.
Generally in process industries, the investment cost for equip-
ment increases as a function of throughput according to the six-
tenths-factor rule, as described below in Eq. (1) (Peterset al., 2004).
In this work, the investment cost used as reference is calculated
with the CCS flow fed, namely, 1.176 kg s−1 . Additionally, the sur-
rogate models have been developed for the same flow. However,
due to the fact that the model that has a generic perspective, the
six-tenths-factor rule is used in order to ensure its applicability to
any feedstock flow.
 0 , 6
Capacity 1
Cost Equip. 1 = Cost Equip. 2 ∗
Capacity 2
The nonlinear cost-size equations are linearized formulating a
piecewise linear approximation (Floudas, 1995). Table 6 indicates
the constants of linearized cost functions that represent the in-
vestment cost for each process unit considered in CCS biorefinery.
For pretreatment stage, the investment cost equation of each pro-
cess unit is given as a function of the feedstock flow. Meanwhile,
in reaction and separation stages, the investment cost equation is
in function of the main product(s) flow.
45
4. Discussion of results
In the CCS biorefinery, the model is formulated as a MINLP con-
taining 3243 equations, 7191 continuous variables and 27 binary
decisions. The solutions and results are presented in the next sub-
sections, with respective description and discussion.
4.1. Alternative solutions
When the optimization problem is solved, the model selects
ethanol as the main product, where the optimal and integrated
biorefinery configuration is composed by the following process
units, size reduction I and II, dilute acid hydrolysis and detoxi-
fication, enzymatic hydrolysis, fermentation using Z. mobilis and
ethanol purification I. Fig. 5 indicates the flowsheet for the base
case. In the distribution of the feedstock input flow toward pro-
cess units of size reduction I and II, the model determines that the
mass flows corresponds to 46.68% and 53.31% of CCS total flow,
respectively. This distribution allows the most suitable interaction
between ethanol process and cogeneration system, which the sup-
plies energy requirements of the biorefinery. In the distribution of
the sugar platforms (C5 and C6 sugars), the model chooses that
the total xylose and glucose flows produced in pretreatment stage
and enzymatic hydrolysis are used for the ethanolic fermentation,
it means that, split of mass fraction, S3 and S4 are equal to 1 (see,
Appendix A). Ethanol biorefinery requires 0.068 MJ s−1 of electri-
cal energy and 1.184 kg of LPS s−1 . The cogeneration system cov-
(1)
ers these demands generating electricity, LPS, MPS and HPS with
flows of, 6.761 MJ s−1 , 1.184, 1.184 and 0.593 kilograms s−1 , respec-
tively. The difference between produced and required energy (elec-
trical and thermal) is considered as additional biorefinery products,
namely, electricity, MPS and HPS. Additionally, CCS biorefinery con-
figuration generates a wastewater flow of 0.009 m3 s−1 .
For the base case, the yields for ethanol, LPS, MPS, HPS
and electricity are 166.52 L, 1888.94 kg, 1888.94 kg, 946.06 kg and
8308.78 MJ per ton of CCS, respectively. The ethanol yield for the
base case of CCS biorefinery is comparable with values reported
46 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53

Table 4
Information about process units of cogeneration system.

Technology Operating conditions Reference

Gasification
Gas turbine (Brayton cycle)
Heat recovery steam generator (HRSG)
CHAR: C and TAR: C6 H6 (benzene) (García Velásquez, 2016; Sharma, 2011)
Pyrolysis
600 °C and 1 bar
Fractional CHAR yield
Cellulose: 0.05
Hemicellulose: 0.10
Lignin: 0.55
Empirical mass ratios
7730.317 5019898
YCO/C O2 = e−1.8447896+ T + T 2
YH2 O/C O2 = 1
YC H4 /C O2 = 5 ∗ 10−16 T 5.6
Pyrolytic decomposition
Cel l ul ose : C6 H10 O5 → 0.675CHAR + 1.754CO + 0, 7305C O2 +
0.6498H2 + 1.785H2 O + 0.7636C H4 + 0, 3461T AR
Hemicellulose: C5 H8 O4
→ 1.1CHAR + 1.403CO + 0.5844C O2 + 0.6999H2 + 1.428H2 O +
0.6109C H4 + 0.2169T AR
Lignin : C7.3 H13.9 O1.3 → 5.61CHAR + 0.4561CO + 0.1899C O2 +
5.666H2 + 0.464H2 O + 0.1985C H4 + 0.1409T AR
Oxidation
Air composition (mass fraction): gasifying agent
CO2 : 0.0 0 05, O2 : 0.2314, N2 : 0.7553 and Ar: 0.0128
1.0 kg wood + 1.5 kg air → 2.5 kg syngas
>800 °C and 1 bar
H2 + 0.5O2 → H2 O
CO + 0.5O2 → C O2
C H4 + 1.5O2 → CO + 2H2 O
T AR + 4.5O2 → 6CO + 3H2 O
CHAR + 0.5O2 → CO
Reduction
<800 °C and 1 bar
C + C O2 ↔ 2CO
C + H2 O ↔ CO + H2
C + 2H2 ↔ C H4
C H4 + H2 O ↔ CO + 3H2
Syngas composition (mole fraction)
CO: 0.2894; CO2 : 0.0537, H2 : 0.2625, H2 O: 0.0368, CH4 :
0.0029 and N2 : 0.3544
Compression (Razak, 2007; Vidal and Martín, 2015)
Pressure ratio 10, isentropic efficiency 85% and air–fuel ratio
6.4 (at 14.85 °C and 1 bar)
Furnace
875 °C and 97.98 bar
Turbine
Pressure ratio 0.2 and isentropic efficiency 90%
2.47 kg syngas/kg CCS and 1.2131 kW/kg syngas
Furnace (Varbanov et al., 2014; Zheng and Furimsky, 2003)
900 °C and 3.6 bar
Low pressure steam (LPS): 145 °C and 3 bar
Medium pressure steam (MPS): 245 °C and 30 bar
High pressure steam (HPS): 285 °C and 60 bar
0.765kg LPS/kg syngas, 0.765kg MPS/kg syngas and
0.383kg HPS/kg syngas

Fig. 5. Flowsheet of the optimal and integrated biorefinery (base case).

 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53 47

Table 5
Costs and selling prices of compounds and utilities.

Compounds Unit Price References

Coffee cut-stems USD/kg 0.024 Calculated

Cooling water USD/kg 0.00125 (García Velásquez, 2016)
H2 SO4 USD/kg 0.094 (ICIS Chemical Pricing, 2010)
Ca(OH)2 USD/kg 0.050 (ICIS Chemical Pricing, 2010)
NaOH USD/kg 0.350 (ICIS Chemical Pricing, 2010)
KOH USD/kg 0.750 (Alibaba, 2018)
Ethanol USD/kg 0.887 (Federación Nacional de Biocombustibles de Colombia, 2018)
NH3 USD/kg 0.386 (ICIS Chemical Pricing, 2010)
Enzyme 1 (Cellulase) USD/kg 0.700 (Moncada et al., 2016b)
CrCl3 USD/kg 2.600 (Alibaba, 2018)
HCl USD/kg 0.200 (Martín and Grossmann, 2016)
NaCl USD/kg 0.100 (Martín and Grossmann, 2016)
Butanol USD/kg 1.230 (Martín and Grossmann, 2016)
HMF USD/kg 2.0 0 0 (Alibaba, 2018)
Furfural USD/kg 2.0 0 0 (Martín and Grossmann, 2016)
NH4 NO3 USD/kg 0.172 (ICIS Chemical Pricing, 2010)
H3 PO4 USD/kg 0.450 (ICIS Chemical Pricing, 2010)
K3 PO4 USD/kg 1.100 (Alibaba, 2018)
Xylitol USD/kg 3.500 (Alibaba, 2018)
Toluene USD/kg 0.850 (ICIS Chemical Pricing, 2010)
PHB USD/kg 3.750 (Naranjo V, 2014)
Lactic acid USD/kg 1.650 (Alibaba, 2018)
NaOCl USD/kg 0.100 (Naranjo Vasco, 2014)
H2 O2 USD/kg 0.400 (Alibaba, 2018)
Enzyme 2 (Burkholderia sp. PTU9) N.R. N.R. N.R.
Acetone USD/kg 0.970 (ICIS Chemical Pricing, 2010)
Na3 PO4 .12H2 O USD/kg 0.410 (Alibaba, 2018)
Urea USD/kg 0.620 (Alibaba, 2018)
FeCl3 .H2 O USD/kg 0.705 (Alibaba, 2018)
MgSO4 .7H2 O USD/kg 0.087 (Alibaba, 2018)
Utilities
Low pressure steam (LPS) USD/kg 0.00756 (García Velásquez, 2016)
Medium pressure steam (MPS) USD/kg 0.00818 (García Velásquez, 2016)
High pressure steam (HPS) USD/kg 0.00986 (García Velásquez, 2016)
Electricity USD/kWh 0.100 (García Velásquez, 2016)
Ethylene glycol 25% (v/v) USD/kg 0.351 Calculated
Wastewater treatment USD/m3 0.547 (del Villar, 2016)

N.R., nonreported.

in the literature for similar and different process configurations.
For example, Cotana et al. (2014) reported the ethanol produc-
tion from pine wood chip (softwood) with a process configuration
composed by pretreatment with steam explosion, enzymatic hy-
drolysis, fermentation and distillation, obtaining a yield of 134 L of
ethanol per ton of feedstock. Ko et al. (2012) analyzed hardwoods
chips (i.e., Acacia confusa Merr. and Eucalyptus globulus) for ethanol
production with process configuration composed by, steam explo-
sion pretreatment and simultaneous saccharification and fermen-
tation (SSF), obtaining yields for ethanol of 89.63 L per ton of aca-
cia and 82.64 L per ton of eucalypt. Zabed et al. (2017) indicated
potential ethanol yields are 280–285 L per ton for hardwoods. The
yields used in acid and enzymatic hydrolysis, and fermentation
correspond specifically to experiments that used CCS as feedstock
that are found in literature. Comparing the obtained and reported
ethanol yields, is possible to infer that acid hydrolysis is the most
convenient pretreatment than steam explosion, and in the same
way, that the process configuration of separate hydrolysis and fer-
mentation (SHF) is a better option than SSF for this process.
The alternative solution I contemplates electrical and thermal
energy as main products. Split of mass fraction S3 and S4 are fixed
to zero in order to avoid ethanol. The distribution of xylose plat-
form can be carried out in S1 or S2 and the distribution of glu-
cose platform can be addressed to S5, S6 or S7 (see, Appendix A).
However, the model indicates that the energy generation is the
most profitable, making the transition to stand-alone process from
biorefinery configuration. This stand-alone process is composed by
particle size reduction II and cogeneration system, with a process-
ing flow of 1.176 kg of CCS s−1 . Fig. 6 shows the flowsheet for al-
ternative solution I. The process unit for particle size reduction
presents an electricity requirement of 0.016 MJ s−1 , which is cov-
ered by the cogeneration system. The difference between required
and generated electricity is taken as main system product. In this
configuration are obtained the following product yields, 1889.46 kg,
1889.46 kg, 946.43 kg and 10,786.88 MJ per ton of CCS of LPS, MPS,
HPS and electricity, respectively. García et al. (2017b) indicated for
a stand-alone process with similar characteristics to the exposed
it in this alternative solution, a yield of 7090 MJ per ton of CCS,
which is close to the result obtained. The yield generated in a
biorefinery configuration is lower than in a stand-alone process
due to the biorefinery implies the obtaining of additional products,
namely, the feedstock should be distributed for all process units.
Meanwhile, the stand-alone process has a total feedstock flow for
electricity generation. The trend indicates that the number of prod-
ucts is inversely proportional to the electricity yield.
4.2. Economic results
Table 7 shows the costs associated to each alternative solution
of the CCS biorefinery. Costs of feedstock, reagents and solvents,
utilities cost, investment cost, wastewater treatment cost and rev-
enues contribute to compute the objective function of the mathe-
matical model (see, Appendix A). The economic profit for both so-
lutions is negative, namely, both biorefinery configurations are not
cost-effective at the processing scale assessed. However, it is pos-
sible that the biorefineries have a positive performance at higher
processing scales. For the base case, the investment cost represents
the highest contribution to the total cost followed by utilities and
48 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53

Fig. 6. Flowsheet of the optimal and integrated biorefinery (alternative solution I).

Table 6 Table 8
Cost functions (investment cost) for process units of CCS Production costs and economic allocation factors for CCS cases
biorefinery. (see (García-Velásquez et al., 2018) to know the calculation pro-
cedure of economic parameters).
Unit A B
Product Production cost Economic allocation factor
Pretreatment stage
I and II 2618.6 145177 Base case
III 30189 2∗ 106 Ethanol 2.87 USD L−1 0.24
IV 39751 2∗ 106 Electricity 0,115 USD MJ−1 0.70
V 35987 2∗ 106 MPS 0.034 USD kg−1 0.04
VI 25632 1∗ 106 HPS 0.040 USD kg−1 0.02
VII 17820 987973 Alternative solution I
Reaction stage Electricity 0.054 USD MJ−1 0.89
VIII 540644 809991 LPS 0.01461 USD kg−1 0.04
IX 219364 913290 MPS 0.01580 USD kg−1 0.05
X 1∗ 106 3∗ 106 HPS 0.01905 USD kg−1 0.03
XI 810483 2∗ 106
XII 403652 1∗ 106
XIII 1∗ 106 804407
XIV 1∗ 106 412848
XV 1∗ 106 907707 and electricity as products in base case is carried out with the
XVI 2∗ 106 883627 idea of selling them to nearby factories in order to make the most
XVII 450175 671445
of the cogeneration system and reduce the production costs. For
Separation stage the base case, the production cost of ethanol is 2.87 USD L−1 (see,
XVIII 347714 810689
XIX 5∗ 106 8∗ 106
Table 8) and according to Walker (2011), the ethanol production
XX 5∗ 106 1∗ 107 cost from hardwood (Salix) is around 0.57 - 0.84 USD L−1 . As it can
XXI 246301 730423 be seen, the difference between values is significant, however, the
XXII 946708 650157 generation of energy through cogeneration system using biomass
XXIII 4∗ 106 1∗ 106
as fuel cannot be ignored, because this consideration is a plus for
XXIV 7∗ 106 2∗ 106
XXV 4∗ 106 1∗ 106 the CCS biorefinery that makes the process not only more environ-
XXVI 1∗ 106 2∗ 106 mental friendly in comparison with processes that use fossil fuels
Cogeneration system for energy generation but also self-sufficient. If ethanol yield would
XXVII 95963 1∗ 107 be 285 L per ton CCS (potential yield for hardwoods (Zabed et al.,
2017)), the production cost would correspond to 2.37 USD L−1 ,
which represents a reduction of 17.5% over the production cost that
is obtained in base case.
Table 7
Costs associated to each solution of CCS cases (M-USD y−1 ). If the base case has a processing capacity of 360 ton of CCS h−1
(commercial scale) with a yield of 166.52 L of ethanol per ton of
Item Base case Alternative solution I
CCS, the approximate production cost for ethanol, electricity, MPS
Objective function (Economic margin) −23.855 −10.78 and HPS are 0.69 USD L−1 , 0.027 USD MJ−1 , 0.0081 USD kg−1 and
Revenues 7.698 11.56 0.0098 USD kg−1 , respectively. It means that the productions costs
Costs of feedstock, reagents and solvents 4.713 1.01
Utilities cost 11.631 10.90
are lower than sale prices, therefore, the biorefinery presents a
Investment cost 15.067 10.43 promising economic performance with a profit margin of 0.66% ap-
Wastewater treatment cost 0.142 0.00 proximately. In the case of alternative solution I, if the processing
Total costs 31.553 22.34 scale is of 10.6 ton of CCS h−1 (pilot - demonstration scale) the
M-USD, Million dollars. approximate production cost for electricity, LPS, MPS and HPS are
0.027 USD MJ−1 , 0.0074 USD kg−1 , 0.0080 USD kg−1 and 0.0097
USD kg−1 , respectively. From this processing scale, the biorefinery
raw materials cost. These costs are mainly affected by the invest- configuration presents a positive performance with a profit margin
ment cost of cogeneration system (10.149 M-USD y−1 ), the cooling of 1.71% approximately. For larger scales, biorefineries more com-
water cost (5.803 M-USD y−1 ) and enzyme cost (2.989 M-USD y−1 ), petitive are expected.
which represent 60% of total costs. The Biomass Integrated Gasifi- Economic allocation factor is defined as the percentage that
cation Combined Cycle (BIGCC) is used as technology for the co- assumes each product with respect to the total cost of biorefin-
generation system, which involves a large number of equipmentin- ery. For all alternative solutions, base case and I, electricity takes
fluencing directly in the investment cost of both alternative solu- the highest percentage due to the cogeneration system generates
tions. As it can be seen in Table 7, when the cogeneration system a considerable flow of electrical energy in comparison with other
works with a total flow of biomass, the investment cost is 10.43 M- products. In general terms, the economic allocation factor for elec-
USD y−1 . tricity is around 0.70 and 0.89, following ethanol with factor of
Table 8 presents the production costs and economic allocation 0.24 and finally thermal energy products with factors below 0.1
factors for products of each case. The consideration of MPS, HPS (see, Table 8).
 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53 49

5. Conclusions and future research works B. Equality constraints

• Feedstock composition

In this work, a general methodology is proposed for systematic

fi,F ligno = φi,F ligno. f
F
Eq. (A.9)
and optimal design of biorefineries. The main features consist of
the development of surrogate models and of define simulations or Flow per feedstock component
equations based on models as well as the aim of self-production 
of utilities for integrated exploitation of resources. The methodol-
fF = fi,F ligno Eq. (A.10)
i
ogy is generic, flexible, versatile and friendly with the user. The
results show that the ethanol is the desirable product due to the Feedstock total flow
high yields and reasonable utilities consumption.
• Mass balance for pretreatment, reaction and separation
As future research works, the authors propose an analysis of
stages
processing scale and a social assessment, a study about the sup-

ply chain of Coffee Cut-Stems (CCS) in Colombia, an experimental IN
fi,k = fi,k (A.11)
assessment of pretreatments and enzymatic hydrolysis to CCS and k
an environmental assessment of biorefineries from CCS using Life
Cycle Assessment (LCA), among others. Inlet unit
Ad,1
fi,k = μi,k . f F (A.12)
Acknowledgments
Added components for main reaction 1
The authors express their acknowledgments to Departamento  
S1
fi,k = αS1, F
i, ligno,k . f i, ligno
F
+ fRem Ad,1
+ fi,k (A.13)
Administrativo de Ciencia, Tecnología e Innovación (Colciencias)
call 727 of 2015. The authors express their acknowledgments to Main reaction 1
research group in Process engineering and sustainable products  
F
fRem = fi,F ligno − αS1, F
i, ligno,k . f i, ligno (A.14)
(PSEM3) of Departamento de Ingeniería Química y Textil of Uni-
versidad de Salamanca, Salamanca – Spain. The authors express Remaining feedstock flow
their acknowledgments to Convocatoria Nacional para el Apoyo a Liq1
fi,k = xLiq1 . fi,k
S1
(A.15)
la Movilidad Internacional de la Universidad Nacional de Colombia
2017–2018. Filter 1
fi,Sol1 F
ligno,k = f Rem (A.16)
Supplementary materials
Solids flow 1
Supplementary material associated with this article can be MW Reag
Reag,1 Ad,1
found, in the online version, at doi:10.1016/j.compchemeng.2019. fi,k = fi,k . (A.17)
MW Ad,1
03.038.
Reagents for secondary reaction
Appendix A. The model  γi,r,k MWi
R
fi,k Liq1
= fi,k + fi,k .θr,k .
Ad,1 Ad,1
. (A.18)
γi,r,k MW Ad,1
Secondary reaction
A. Objective function Liq2
fi,k = xLiq2 . fi,k
R
(A.19)
Z = SProd − C F − C Reag − CUtil − C ww − C Inv (A.1)
Filter 2
where:  
 Sol2
fi,k = 1 − xLiq2 . fi,k
R
(A.20)
SProd = P rkP . fi, k (A.2)
k i Solids flow 2
Product sales Ad,2
fi,k = δi,k . fi,k
Liq2
(A.21)
F F F
C = Pr . f (A.3) Added components for main reaction 2
Feedstock cost MW Reag
  Reag,2
fi,k Liq2
= fi,k . (A.22)
CC = P rkReag . fi,k
Reag
+ P rkAd . fi,k
Ad
(A.4) MWi
k i k i
Reagents for main reaction 2
Reagents and added components cost 
 γi,r,k MWi
P1
fi,k Ad,2
= fi,k Liq2
+ fi,k + fi,k .θr,k .
Liq2 Liq2
. (A.23)
CUtil = βkUtil .PrUtil
k .f
F
(A.5) γi,r,k MW Liq2
i
k Util
Main reaction 2
Utilities cost
 P1,OUT
fi,k P1
= fi,k .σi,k (A.24)
C ww = P rkw . w
fi,k (A.6)
k i Product separation 1
Wastewater management cost w1,OUT P1 P1,Out
 fi,k = fi,k − fi,k (A.25)
C Inv = Invk (A.7)
Waste separation 1
k

Investment cost
Ad,3
fi,k = δi,k . fi,ligno,k
Sol1
(A.26)
F
Invk = Ak . f + Bk (A.8) Added components for main reaction 3
 
Investment cost, linearized S2
fi,k = αS2, Sol1
i, ligno,k . f i, ligno,k
Sol1
+ fRem Ad,3
+ fi,k (A.27)
50 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53

Table A1
Information about the superstructure of CCS biorefinery.

Component Description Component Description

Process units XIX, y19 Furfural purification I

I, y1 Size reduction (0.4 mm) XX, y20 Furfural purification II
II, y2 Size reduction (5–10 mm) XXI, y21 Ethanol purification I
III, y3 Dilute-acid hydrolysis and detoxification XXII, y22 Ethanol purification II
IV, y4 Alkaline hydrolysis and detoxification XXIII, y23 PHB purification
V, y5 Organosolv XXIV, y24 AB purification
VI, y6 Liquid hot water XXV, y25 ABE purification
VII, y7 Ammonia fiber explosion XXVI, y26 Lactic acid purification
VIII, y8 Enzymatic hydrolysis XXVII, y27 Cogeneration system
IX, y9 C. guilliermondii fermentation Sources
X, y10 Dehydration with HCl Src1 Feedstock resource
XI, y11 Dehydration with H2 SO4 Src2 Sulfuric acid resource
XII, y12 Z. mobilis fermentation Src3 Water source
XIII y13 S. cerevisiae fermentation Src4 Calcium hydroxide source
XIV, y14 B. megaterium fermentation Src5 Sulfuric acid source
XV, y15 C. beijerinckii fermentation Src6 Potassium hydroxide source
XVI, y16 C. acetobutylicum fermentation Src7 Water source
XVII, y17 E. coli fermentation Src8 Phosphoric acid source
XVIII, y18 Xylitol purification Src9 Ethanol source
Src10 Water source Src32 Xylitol source
Src11 Sulfuric acid source Src33 Sodium hypochlorite source
Src12 Ethanol source Src34 Enzyme 2 ((Burkholderia sp. PTU9)) source
Src13 Water source Src35 Hydrogen peroxide source
Src14 Water source Src36 Water source
Src15 Water source Src37 Calcium hydroxide source
Src16 Ammonia source Src38 Water source
Src17 Water source Src39 Water source
Src18 Water source Src40 Sulfuric acid source
Src19 Water source Src41 Water source
Src20 Enzyme 1 (Cellulase) source Src42 Water source
Src21 Chromium chloride (III) source Src43 Air source
Src22 Hydrochloric acid source Src44 Air source
Src23 Sodium chloride source Src45 Water source
Src24 Butanol source Mixers
Src25 Sodium hydroxide source Mix1 Liquid streams mixer from pretreatment stage
Src26 Sodium chloride source Mix3 Glucose and xylose mixer
Src27 Butanol source Mix4 Wastewater streams mixer
Src28 Sulfuric acid source Mix5 Required electricity mixer
Src29 Calcium hydroxide source Mix6 Required LPS mixer
Src30 Ammonium nitrate source Mix7 Required MPS mixer
Src31 Air source Mix8 Required HPS mixer
Splitters
Spl1 Feedstock splitter I
Spl2 Feedstock splitter II
Spl3 Xylose splitter
Spl4 Glucose splitter
Spl5 Glucose splitter to ethanol production
Spl6 Xylose splitter to furfural production

Main reaction 3 Main reaction 3

 
Sol1
= fi,Sol1 αS2, Sol1 P2,OUT
fi,k P2
= fi,k . i,k (A.34)
fRem ligno − i, ligno,k . f i, ligno,k (A.28)

Remaining solids flow Product separation 2

w2,OUT P2 P2,Out
fi,Sol3 Sol1 fi,k = fi,k − fi,k (A.35)
ligno,k = f Rem (A.29)
For utilities
Solids flow 3
Liq3 fkUtil1 = βkUtil1 . f F (A.36)
fi,k = xLiq3 . fi,k
S2
(A.30)
Utilities for pretreatment stage
Filter 3
fkUtil2 = βkUtil2 . f F (A.37)
Ad,4
fi,k = δi,k . fi,k
Liq3
(A.31)
Utilities for main reactor 1
Added components for main reaction 4 fkUtil3 = βkUtil3 . f F (A.38)
Reag
Reag,3 Liq3 MW Utilities for separation 1
fi,k = fi,k . (A.32)
MWi
fkUtil4 = βkUtil4 . f F (A.39)
Reagents for main reaction 4
Utilities for main reactor 2
 γi,r,k MWi
P2
fi,k = Ad,4
fi,k + Liq3
fi,k + fi,k θ
Liq3 Liq3
. r,k . . (A.33) fkUtil5 = βkUtil5 . f F (A.40)
γi,r,k MW Liq3
i
 V. Aristizábal-Marulanda, C.A. Cardona Alzate and M. Martín / Computers and Chemical Engineering 126 (2019) 35–53 51

Utilities for main reactor 3 Appendix B. MINLP problem structure

fkUtil6 = βkUtil6 . f F (A.41) The general MINLP formulation is the following:

Utilities to separation 2 minx,y z = f (x, y )
fkUtil = fkUtil1 + fkUtil2 + fkUtil3 + fkUtil4 + fkUtil5 + fkUtil6 (A.42)
s.t. h(x, y ) = 0
Total utilities consumption in the unit

C. Inequality constraints g(x, y ) ≤ 0

• Connection equations

Liq2
fi,k = Sn . fi,k (A.43) x ε n , y ∈ {0, 1}m
Xylose flow rate where:

S1 + S2 + S3 = 1 (A.44) z: represents the objective function (e.g., annualized total cost)

x: is a vector of n continuous variables (e.g., composition, flows,
Mass fraction in xylose distribution
prices)
Liq3
fi,k = Sn . fi,k (A.45) y: is a vector of integer variables (e.g., alternative reagents or
solvents)
Glucose flow rate h(x, y ) = 0 denotes the m linear or non-linear equality con-
strains (e.g., mass and energy balance)
S4 + S5 + S6 + S7 = 1 (A.46)
g(x, y) ≤ 0 represents the p linear or non-linear inequality con-
Mass fraction in glucose distribution strains (e.g., feasibility constrains and logical constrains)
Sn parameter is the mass fraction of xylose or glucose in the
sugars distribution and its value can be between 0 and 1. The sub-
script can be 1 to 3 for xylose distribution and 4 to 7 for glucose
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