pubs.acs.

org/IECR Article

Integrated Methodology for Optimal Synthesis of Lignocellulosic

Biomass-to-Liquid Fuel Production Processes: 2. Superstructure
MINLP Modeling and Evaluation for Optimal Biofuel Process
Synthesis and Integration
Paola Ibarra-Gonzalez and Ben-Guang Rong*
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ABSTRACT: For thermochemical conversion routes to BtL fuel production, in part 1, we have developed a framework for the
synthesis of a BtL superstructure that was formulated by the interconnection of processing blocks consisting of unit operations
belonging to five base case process routes along with the data and information prepared for the embedded processing blocks. In part
2, a mixed integer nonlinear programming (MINLP) model is implemented for the superstructure optimization. The superstructure
is defined as an MINLP problem coded in GAMS 24.5.6, which sets the objective to minimize the total cost of manufacturing
(TCOM) of BtL fuels under different cases and integration scenarios. Three cases are demonstrated for three different product
profiles, and three network flowsheets are obtained as optimal technology routes. The three optimal network flowsheets are then
rigorously simulated and compared with the base case process flowsheets. The results demonstrated that this methodology can
generate optimal BtL biofuel production processes under different product scenarios.

1. INTRODUCTION costs. As in process synthesis, a consensus is that, if the optimal

Currently, various process routes to produce liquid and
gaseous fuels from lignocellulosic biomass have been explored,
and it has been proven that the properties of these biomass-to-
liquid (BtL) fuels can comply with the regulated fuel quality
standards.1−3 BtL fuel conversion routes and plant config-
urations can vary quite extensively and can be adapted
according to product specifications. For instance, production
of advanced biofuels via gasification followed by Fischer−
Tropsch (FT) synthesis is receiving increased attention due to
the high-quality fuels produced. This process route produces
fuel components compatible with conventional fossil fuels.
However, the high investment associated with its commercial
application makes this option economically unfeasible.4 For
this reason, other process routes such as pyrolysis followed by
hydroprocessing and/or catalytic cracking, as well as different
configurations for the gasification-FT route, should be
explored, primarily aiming to lower investment and production
flowsheet is not predefined, it will not be found. Thus, the BtL
process configurations cannot be limited to a certain number.
Each biofuel technological route can be considered as an
individual concept, and customized designs can be explored.
From process point of view, other alternative to improve the
processes is the coprocessing combining two or more
feedstocks or technologies. In previous studies, the application
of coprocessing has been proposed. For instance, Baliban et
al.5 proposed the thermochemical conversion of biomass and
natural gas to liquid fuels, such as, gasoline, diesel, and
Received: June 10, 2020
Revised: July 22, 2020
Accepted: July 23, 2020
Published: July 23, 2020

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.iecr.0c02903

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Figure 1. Systematic procedure for superstructure MINLP modeling and evaluation for optimal biofuel process synthesis.

kerosene with simultaneous heat, power, and water integration. of using lower-cost fossil-based feedstocks, it may not always
The results suggested that these systems can be economically be practical to utilize multiple feedstocks within a single
competitive with petroleum-based processes. Even though refinery. The reason is that the distributed network of biomass
hybrid-feedstock refineries can take advantage of the benefits feedstock locations will contain several points where the
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infrastructure for coal or natural gas delivery is minimal or
nonexistent.6 Moreover, coprocessing of biomass and natural
gas achieved only 50% emissions reduction because a major
component of the life-cycle emissions is attributed to
combustion of the liquid fuels.5
The selection of the most promising BtL fuel process
configurations depends on the raw material availability,
location, plant capacity, conversion steps for total production
processes, desired products and relevant by-products, as well as
the state of technical development, and overall production
costs. Moreover, the interaction of all these variables plays an
important role in why and how certain biofuel production
processes are more successful than others. Santibañez-Aguilar
et al.7 proposed a mathematical programming model for the
optimal design of a supply chain of biorefineries to produce
ethanol and biodiesel, which considers the uncertainty in the
prices of raw materials. In another work by Santibañez-Aguilar
et al.,8 the focus was on a MINLP optimization problem to
propose the optimal supply chain design considering the
harvesting sites, availability of the biomass sources, processing
plants geographical location, demand of products in each
market, location of storage facilities, and transportation
between these components.
From the different issues that need to be considered to select
the most promising BtL biorefinery design, in this work, the
focus is on the technical development and production costs.
This work, instead of focusing on the evaluation of one process
route at once, proposes the development of a superstructure
for producing liquid hydrocarbon fuels from lignocellulosic
biomass to generate new process systems, which may increase
the feasibility of these technologies by reducing the high-
investment cost associated with its application.
Process synthesis strategies capable of generating and
evaluating promising process alternatives under different
constraints and specifications have been recently developed
in a fully automated and computationally efficient way. For
instance, Martiń and Grossman9 proposed a superstructure for
the production of diesel from switchgrass via gasification
followed by FT. The optimization of the system was
formulated as a mixed-integer nonlinear programming
(MINLP) problem for the optimal production of FT-diesel
while minimizing the energy and hydrogen consumption.
Baliban et al.6,10 proposed an optimization-based process
synthesis capable of analyzing distinct process designs of a
hardwood BtL refinery considering the gasification of biomass
and FT hydrocarbons synthesis. Torres-Ortega et al.11,12
defined a synthesis network superstructure based on rigorous
simulations and a MINLP using simplified model to optimize
the integrated production of biodiesel and hydrotreated
vegetable oil diesel. It was observed that the previous works
use estimates from several literature sources with simplified
models for the unit operation costs and energy cost evaluation.
For such process synthesis and evaluation, it is important to
use rigorous and consistent data and information including
technical and economic data for both operation units and
process flowsheets. Moreover, integrated rigorous simulation
and mathematical techniques to optimize and synthesize new
process routes have shown to simultaneously determine
different design aspects that increase the feasibility of
processes. For instance, Caballero et al.13 presented a
superstructure-based optimization that combines integrated
mathematical programming techniques and rigorous simu-
lations to select the design parameters that minimize the total
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investment and operation cost of different distillation column
designs. To our knowledge, this work is the first to consider
simultaneously different thermochemical-based process tech-
nologies with consistent rigorous simulations as performance
and cost sources for the superstructure formulation as well as
for the posterior MINLP optimization to evaluate different
process designs under different product profile scenarios. The
simultaneous optimization strategy mathematically guarantees
that the algorithm will evaluate all the process alternatives on
the same basis for both base cases and new process routes and
will generate the process configuration that presents the
minimal cost of the BtL production and meets product
requirements.
This study is to develop a superstructure-based optimization
algorithm for synthesis of softwood BtL processes using
rigorous simulation results as performance and cost sources. In
part 1, the step-by-step formulation of a superstructure by the
combination and interconnection of unit operations was
presented. The process simulator Aspen Plus was used to
generate the consistent and rigorous data of the processing
blocks conforming the BtL process alternatives in the
superstructure. In this part 2, an optimization framework
with MINLP modelling of the superstructure is presented,
which considers different thermochemical-based processes,
feedstock scenarios, product portfolios, and integration
scenarios. The MINLP solution is to generate optimal
alternatives that minimize the total overall process cost and
maximize the biofuel yield.
2. METHODOLOGY FOR SUPERSTRUCTURE MINLP
MODELING AND EVALUATION FOR OPTIMAL
BIOFUEL PROCESS SYNTHESIS
In part 1, a softwood BtL superstructure (Figure S1) was
formulated based on the information collected from the
rigorous simulation of different technological sections
(thermochemical conversion, upgrading section, and separa-
tion section) conforming five base case processes. In this part,
the softwood BtL superstructure is formulated as a MINLP
problem coded in GAMS 24.5.6. Figure 1 presents a systematic
procedure for the mathematical modeling of the super-
structure. For the optimization algorithm setup, first, input
specifications were given in the form of matrices including
processing block numbers and their corresponding feedstocks,
intermediate components, and fluidizing agents flow rates.
Likewise, catalyst and auxiliary reagent ratios and raw material
costs were defined. The input specifications were collected
from literature and the rigorous simulations. Then, processing
block information (number of unit operations, capital costs,
and energy costs) is given in the form of matrices. Mass
balance equations based on the results from the rigorous
simulations in Aspen Plus were specified in the algorithm.
Binary and fractional variables were used to define the
existence or absence of unit operations and to specify the
mass and energy integration possibilities within the processing
blocks. The processing block mass balances together with the
specification of binary and fractional variables allow the
definition of the possible interconnections between processing
blocks. Moreover, to specify the possible integration scenarios,
the mass balances and capital and energy costs of the
wastewater treatment plant and cogeneration plant were
specified.
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Concerning the economic calculations, equations for the
TCOM evaluation included capital costs, operating labor costs,
energy costs, cost of waste disposal, and raw material costs.
For implementation of the algorithm toward specified
product cases, product profile constraints defining the
maximum and/or minimum total desired fuel flow rates were
given. The initial values for product profile constraints were
based on the actual gasoline and diesel flow rates obtained
from the rigorous simulation of the base case processes. Then,
the objective function is defined, which is to minimize the
TCOM of BtL fuels and maximize the productivity under
different constraints and integration scenarios. The boundaries
and initial values for the MINLP solution are given for the
specified case study.
Finally, the optimal MINLP solutions were rigorously
simulated for evaluation and comparison. The comparisons
include product profiles, TCOM with and without integra-
tions, productivity, TCOM per gasoline gallon equivalent, and
product properties.
The advantage of the methodology for simultaneous
optimization is for searching the structure space to obtain
the optimal process with given constraints and specifications.
This cannot be done with the conventional enumerating
approach to design the individual feasible process flowsheet; it
is also different from the numerical optimization for a single-
prescribed process optimization.
3. SUPERSTRUCTURE MASS AND ENERGY
INTEGRATION
In part 1, processing blocks were defined and interconnected
into a superstructure. Besides considering block combination,
the mass and energy integration between the unit operations
conforming the processing blocks can be explored. In a
previous study by Ibarra-Gonzalez and Rong,14 the liquid, gas,
and solid emissions of the five base case process routes were
reported and it was found that important amounts of gases and
water are produced or wasted through the processes.
Therefore, process integration techniques can be implemented
to reduce the liquid emissions and overall energy consumption
of the process routes. Moreover, cogeneration through
combined heat and power is another integration option. The
integration possibilities are described in the following sections.
3.1. Process Water Integration. BtL processes require
high amounts of water. For instance, during bio-oil and syngas
production, an excessive amount of water is required for
product condensation and cleaning. Therefore, in the
pyrolysis-based routes, water coming from the quench columns
employed in the cooling and recovery of the pyrolysis oil could
be processed and recycled back to the quench columns.
Additionally, in the gasification-based routes, the wastewater
stream coming from the scrubber can be purified (contains
ammonia and CO2) and sent back to the scrubber.
3.2. Gases Integration. During the pyrolysis reaction,
NCGs are usually employed as fluidizing agents to increase the
formation rates of the pyrolysis products. These gases (mainly
CO, CO2, CH4, H2, C2H4, and C2H6) are also produced
through the process and thus can be potentially recovered and
recycled to the pyrolysis reactor. On the other hand, fuel gases
such as methane, ethane, and propylene produced in both the
pyrolysis-based and gasification-based process routes can be
sent to a cogeneration plant for power generation.
3.3. Heat Integration. The general objective is to reduce
heat requirements in the process, which can be achieved by
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utilizing part of the wastewater process streams to generate and
provide energy for the system. Thus, in the cogeneration plant,
pure water coming from the processes can be sent to the steam
generation section where the water can be directed to a
pressure boiler to produce steam. Part of the steam can be used
for heating purposes, and the other part can be sent to the
electricity generation section (described in section 3.4.).
Simultaneously, the fuel gases (methane, ethane, and
propylene) can be compressed and burned to produce the
heat required to increase the water temperature and produce
steam.
3.4. Electricity Integration. In the cogeneration plant,
steam and gas turbines can be employed to produce the
electricity required by the processing blocks. For instance, a
fraction of the steam produced in the pressure boiler, described
in section 3.3, can be sent to a steam turbine to produce
electricity. Moreover, the fuel gases used to increase the water
temperature in section 3.3 can be further sent to a gas turbine
to generate additional electricity. The total electricity demand
of each of the gasification-based and pyrolysis-based process
routes can be supplied with the electricity generated in the
steam and gas turbines.
4. SUPERSTRUCTURE MATHEMATICAL MODELING
From the superstructure and integration possibilities, the
synthesis and evaluation of technological routes and
integration scenarios are determined with algorithms that are
able to handle complicated nonlinear and continuous problems
with given constraints. The optimization of mass and energy
transfer between processing blocks is addressed by MINLP in
which the TCOM of the BtL fuel production processes is
minimized and the biofuel production is maximized.
The MINLP model rigorously describes the input−output
relationships of each processing block within the super-
structure. The MINLP modeling consists of specifying the
input (feedstocks, model compounds, auxiliary streams, flow
rates, conversion factors, recovery factors, etc.) and output
(desired products, minimum outlet flow rates, etc.) stream data
collected from the rigorous simulations and the equations that
define the interconnection between the thermochemical
conversion, upgrading, and separation processing blocks that
convert the inputs into the desired outputs, while meeting the
objective function.
Accordingly, the synthesis process can be decomposed into
two levels. On the first level, the optimization problem selects
the technological routes, which implies discrete decisions. On
the second level, the decision on how these technologies
should be interconnected is performed in a continuous space.
The equations used to represent the BtL processing super-
structure are mass balances, economics, capacity adjustments,
etc., which are sets of linear and nonlinear equations. For
instance, some of the nonlinearities are due to the definition of
the separation blocks where stream splits are included as well
as in the economic blocks. Considering this, it is clear that the
optimal process route synthesis involves a discrete-continuous
nonlinear problem.
4.1. Superstructure MINLP Algorithm Setup. As
described before, the BtL processing superstructure algorithm
consists of the specification of input and output streams and
processing block parameters, which are defined, based on data
collected from the simulations (mass and energy balances,
emissions, processing blocks capital and energy costs,
economic constraints, and product profile constraints). After
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Table 1. Conversion Factor Convf(i,j,k) Matrix Table
the definition of the overall process inputs and outputs, the
equations to describe the superstructure are specified in the
GAMS algorithm. These equations are the objective function,
mass component balances, integrations (gases, water and
cogeneration), waste streams, and economic calculations
(capital cost, energy cost, waste disposal cost, operating labor
cost, and raw material costs), which are given as follows.
4.1.1. Parameter Specification. For the algorithm setup, all
the input information was specified as a set of matrix tables.
First, feedstock flow rates and market prices for raw materials,
utilities, and intermediate chemicals were defined, as presented
in Table S1. Then, processing block performance parameters
such as conversion and separation factors were defined. In
Table 1, an example of how the matrix tables were given in the
algorithm is presented. The term Convf(i,j,k) refers to the
conversion factors where, as introduced in part 1, the index i
refers to the number of processing block (1, 2, 3, ...n), j refers
to the technology option (1, refers to feedstock selection; 2, for
a reaction block; or 3, for a separation block), and k refers to
the component being consumed or produced. In total 66
components were considered among all the process streams. In
Table 1, the term x represents the conversion factor value,
which takes negative values (−x) if the component is being
consumed or positive values (x) if is being produced. For
instance, the performance parameters for the gasification-low
temperature FT (LTFT)-upgrading processing blocks, calcu-
lated in Part 1 of this work, are presented in Tables S2 and S3.
Besides these parameters, in another matrix table, auxiliary
reagent ratios (fluidizing agents, catalysts, solvents, etc.) were
given. For the economic calculations, in other four matrix
tables, the numbers of unit operations, capital costs, electricity,
and thermal costs of each reaction, and separation block were
specified. Likewise, the number of unit operations of the
cogeneration and wastewater treatment plant and their
respective capital and energy costs were included.
4.1.2. Objective Function. The objective is to determine the
optimal processing route within the superstructure under
specified constraints and product portfolios, which minimizes
the TCOM of BtL fuel systems and maximizes the
productivity. The objective function was defined as a relation
of these two variables in the form of eq 1
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minimize TCOM GGE
TCOM
=
productivity
0.280CCtot + 2.73COL + 1.23(ECtot + C WT + C RM)
=
productivity
(1)
where TCOMGGE is the TCOM per gasoline gallon equivalent
(GGE), CCtot is the total capital cost of the plant, COL is the
cost of operating labor, ECtot is the total cost of utilities of
energy cost, CWT is the cost of waste treatment and disposal,
and CRM is the raw material cost. The equations for the
economic calculations will be introduced in section 4.2. The
term productivity stands for the GGE produced per year, as
depicted in eq 2. By introducing the term productivity to the
equation, it is guaranteed that the total product flow rate is
being maximized, and the manufacturing costs are minimized.
productivity = ∑ [fuel product flow rate·GGE]·OY (2)
The fuel product flow rate values calculated in kilograms per
hour are then converted to gallons. Then, the results are
multiplied by the gasoline and diesel GGE values and an
operational year (OY) consisting of 8000 h is considered.
4.1.3. Mass Balances. The mass balances show the key
inputs and outputs of the superstructure blocks. In part 1 of
this study, the processing blocks that were interconnected into
the superstructure were identified with specific tags, as
presented in Figure S1. For instance, the reaction blocks
were tagged as RXN(i,j) and the separation blocks as SEP(i,j).
In these tags, the index i refers to the processing block number
and j to the technology option (1, refers to feedstock selection;
2, for a reaction block; or 3, for a separation block). However,
to describe the performance of each processing block, a new
index k is introduced when the mass balances are concerned.
The index k represents the components (e.g., k = 1 is the
softwood, k = 2 is CO, k = 3 is CO2, etc.). A total of 66
components including feedstock, solvents, fluidizing gas, and
so on were considered. The values of the index k are defined in
the matrix tables, and with them, the mass flow rate per hour of
each component can be calculated. Moreover, in Figure S1, a
subscript LB was given to the lumped-process blocks (set of
individual reaction and separation process blocks grouped into
one major block as a functional process section) to
differentiate them from the individual process blocks.
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Figure 2. Fractional variables (Yn) to define interconnections between the thermochemical conversion blocks and upgrading blocks.
However, in the algorithm setup, there is no need to define the
blocks with subscripts.
Furthermore, as can be observed in Figure S1, each lumped-
process block consists of a reaction block and separation block,
and therefore, separate mass balances for each lumped-reaction
block and lumped-separation block are carried out. The mass
balance equations for the reaction blocks in the conversion
section (PYR and GAS) are in the form of eqs 3 and 4.
min(RXN(i , j , k)) = m feedstock(RXN(i , j , k)) + mnew(RXN(i , j , k))
mout(RXN(i , j , k)) = min(RXN(i , j , k)) + min(RXN(i , j ,‘k ’))
·Convf (RXN(i , j ,‘k ’))
where min(RXN(i, j, k)) is the reaction block total inlet flow rate in
kilograms per hour, mfeedstock(RXN(i, j, k)) is the mass flow rate of
spruce and/or pine residues, mnew(RXN(i, j, k)) is the auxiliary
stream flow rate, such as, catalysts, hydrogen, steam, sand,
fluidizing gas, and so on. The auxiliary stream flow rate
mnew(RXN(i, j, k)) is calculated with eq 5, and it is equal to the
feedstock flow rate times the new stream component ratio
Newf(RXN(i, j, k)). As depicted in eq 4, the term mout(RXN(i, j, k))
stands for the total outlet flow rate, which is equal to the inlet
flow rate plus the limiting reagent ‘k’ inlet flow rate times the
conversion factor Convf(RXN(i, j, ‘k’)). This factor represents the
conversion of reagents to products
mnew(RXN(i , j , k)) = Newf(RXN(i , j , k))·mfeedstock
For the subsequent individual reaction blocks and lumped-
reaction blocks belonging to an upgrading section, the mass
balances are in the form of eqs 6 and 7 where the total inlet
flow rate of the reaction block min(RXN(i, j, k)) is equal to the
outlet flow rate moutPB coming from a previous block (reaction
(mout(RXN(i, j, k))) or separation (moutn(SEP(i, j, k)))) plus the
auxiliary stream mnew(RXN(i, j, k)), which refers to catalysts and
other auxiliary reagents. On the other hand, the outlet flow rate
of a reaction block mout(RXN(i, j, k)) is equal to its inlet flow rate
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plus the inlet flow rate of the limiting reagent ‘k’ times the
conversion factor, as presented in eq 7.
min(RXN(i , j , k)) = moutPB + mnew(RXN(i , j , k)) (6)
mout(RXN(i , j , k)) = min(RXN(i , j , k)) + min(RXN(i , j ,‘k ’))
·Convf (RXN(i , j ,‘k ’))
(7)
Concerning the separation block mass balances, as depicted
(3)
in eqs 8 and 9, the block inlet flow rate min(SEP(i, j, k)) is equal to
the previous block flow rate moutPB plus the auxiliary stream
flow rate mnew(SEP(i, j, k)). The term mnew(SEP(i, j, k)) is only defined
when an extra reagent stream is required (e.g., water needed
(4) for scrubbing). On the other hand, the separation block outlet
flow rate mout(SEP(i, j, k)) is equal to the sum of the separation
block outlet streams moutn (n = 1,2,3, ...)
min(SEP(i , j , k)) = moutPB + mnew(SEP(i , j , k)) (8)
mout(SEP(i , j , k)) = mout1(SEP(i , j , k)) + mout 2(SEP(i , j , k)) +
... + moutn(SEP(i , j , k)) (9)
In addition, from the separation unit rigorous simulations,
separation or recovery factors Sepf(SEP(i, j, k)) were calculated.
These factors allow to calculate the component mass flow rate
of each separation block outlet stream. These factors are
implicit in the separation block outlet stream term
(5) moutn(SEP(i, j, k)), as presented in eq 10
moutn(SEP(i , j , k)) = min(SEP(i , j , k))·Sepf(SEP(i , j , k)) (10)
4.1.4. Thermochemical Conversion and Upgrading Block
Interconnection. To define possible interconnections, frac-
tional variables Yn are introduced. The term Yn defines the
interconnections between the processing blocks in the
conversion section and following upgrading blocks. This
term indicates the product stream fraction from the
thermochemical conversion section that is to be sent to the
upgrading blocks. For example, as shown in Figure 2, Y1
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indicates the fraction of pyrolysis oil that should be redirected
to the hydroprocessing blocks and Y2 indicates the fraction of
pyrolysis oil going to the catalytic cracking blocks. For the
gasification routes, the terms Y3 and Y4 define the fraction of
syngas being sent to LTFT and/or HTFT, respectively. These
variables can take values from 0 to 1.
4.1.5. Integrations. A term Xn is introduced to define the
possible mass and/or energy integrations. The different levels
of integrations considered for the mathematical modeling are
NCG integration, water integration, and cogeneration. The
general equation to represent the integrations is in the form of
a mass balance where the extra term Xn considering the
integration is introduced, as depicted in eq 11 for a reaction
block. For instance, as defined in eq 11, a stream coming from
a separation block mrec(SEP(i, j, k)) is recycled to a reaction block
min(RXN(i , j , k)) = moutPB + mnew(RXN(i , j , k)) + mrec(SEP(i , j , k))·X n
The term mrec(SEP(i, j, k)) refers to the outlet stream coming
from a separation block, which might be recycled, and the term
Xn decides whether the stream is being recycled or not. An
equation of this form can be also defined for a separation block
if the outlet stream from a separation block mrec(SEP(i, j, k)) is
being recycled also to a separation block (e.g., water recovered
from a distillation column and sent to a scrubber).
The term Xn was defined as an integer variable because more
than the total flow rate of the recycle stream is needed to fulfill
the actual process requirements. Xn takes a value of 1 if the
stream is being recycled or 0 if the stream is considered as
emission. For example, for SEP(1,3)LB in Figure 3, terms like
Figure 3. Integer variables (Xn) to define possible integration of water
stream in SEP(1,3)LB.
X1 and X2 are considered for the water outlet stream in which
the term X1 refers to a possible integration (water recycling to
quenching) and X2 refers to an emission. Since X1 considers
the water integration, this term should be specified in the form
of the integration in eq 11, as shown for this example in eq 12.
On the other hand, the term X2 should be defined in the form
of the waste stream disposal as in eq 14.
min(SEP(1,3, k)) = mout(RXN(1,2, k)) + mnew(SEP(1,3, k))
+ mrec(SEP(1,3, k))·X1
Moreover, an equation to relate the terms X1 and X2 is
introduced, as depicted in eq 13. This means that, if X1 is equal
to 1, then the total stream flow rate is being recycled and by
default, there is no emission and X2 is equal to 0
X1 + X 2 = 1 (13)
4.1.6. Waste Stream Disposal. The separation block outlet
streams that are not sent or being recycled to other blocks are
considered as emissions. The emissions or waste streams can
be quantified with eq 14. In this equation, the term Xn can take
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values of 1 if it is considered as an emission or 0 if it is being
recycled, similar to what was previously explained in section
4.1.5
min(WWD(i , j , k)) = ∑ mout (SEP(i ,j ,k))·Xn
n (14)
4.2. Economic Calculations. The cost associated to the
operation of a BtL plant must be estimated to analyze the
economic feasibility of the proposed process routes. In this
section, the important cost factors related to the calculation of
the TCOM are described.
4.2.1. Capital Cost. The total capital cost of the plant was
calculated from the results of the processing block rigorous
simulations (given as a matrix table in the algorithm) and
considering the Lang factor technique. The total cost is
determined by multiplying the total purchased cost of all the
processing blocks (group of unit operations) involved in the
(11) process by a constant, called the Lang factor. For solid−fluid
processing plants, the Lang factor is equal to 3.63.15 To
calculate the total cost of the plant first, the individual
processing block capital cost should be calculated.
The individual processing block capital cost CCbase(i, j),
which is given in the algorithm, was calculated in an Aspen
process economic analyzer for a base-flow rate mbase, and thus,
an equation to adjust the capital cost CCadj(i, j) depending on
the real mass inlet flow rate min(i, j, k) is introduced for the cases
where a different plant capacity is desired. The capital cost
adjustment is depicted in eq 1515
ij min(i , j , k) yz
= CC base(i , j)jjj zz
j mbase zz
0.6
k {
CCadj(i , j)
(15)
Finally, the total capital cost CCtot of a process route is equal
to the sum of the individual processing block capital cost
divided by the plant lifetime times the Lang factor, as
ij CCadj(i , j) yz
presented in eq 16. As plant lifetime, 20 years were considered.
CCtot = 3.63 ∑ jjj z
j plant lifetime zzz
k { (16)
4.2.2. Energy Cost. The energy cost EC(i, j) described by eq
17 is equal to the utility consumption (amounts of electricity,
steam, and thermal fluids) of each processing block times the
utility cost and plant operating hours. The electricity, heating,
and cooling requirements of each processing block were
calculated with the Aspen process economic analyzer V8.8 in
the form of eq 17 and specified in the algorithm as a matrix
table. The utility consumption and costs were reported in
kilograms or kilowatts per hour and dollars per kilogram or
kilowatt, respectively. For the plant operation, 8000 h was
considered per year (OY).
EC(i , j) = utility consumption· utility cost ·OY (17)
(12)
The total energy cost ECtot of a process route is equal to the
sum of the individual energy cost of the processing blocks, as
shown in eq 18
ECtot = ∑ EC(i ,j) (18)
4.2.3. Operating Labor Cost. The operating labor costs COL
calculation considers the necessary operating labor OL and
their corresponding salary per year, as depicted in eq 19. It was
assumed that each operator is paid 25.33 dollars per hour and
works in total 2000 h per year16
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Figure 4. MINLP algorithm implementation and solution.
COL = OL· annual salary (19)
The operating labor OL is equal to the number of operators
needed per shift NOL times the number of shifts per day. In eq
20, the NOL calculation is presented.15 In this study, four shifts
of 6 h were assumed
NOL = (6.29 + 31.7P 2 + 0.23Nnp(i , j))0.5
(20)
where P is the number of processing steps involving the
handling of solids, such as grinding and solid removal, and
Nnp(i, j) is the number of unit operations included in each
processing block, such as, compressors, separation units,
reactors, and heat exchangers. For the operating labor
calculation, the definition of a matrix table including the
number of unit operations of each reaction and separation
block was required.
4.2.4. Waste Disposal Costs. The waste disposal costs are
calculated based on the emissions stream flow rate
min(WWD(i, j, k)), which are not recycled to the BtL plant. The
total waste disposal cost is the multiplication of the wastes flow
rate (kilograms per hour) times the disposal costs DC(dollars
per kilogram) and considering that an OY consists of 8000 h,
as presented in eq 21
C WT = min(WWD(i , j , k))·DC ·OY (21)
4.2.5. Raw Material Costs. The total raw material cost CRM
is equal to the sum of the feedstock flow rate mfeedstock(RXN(i, j, k))
and the new stream flow rate mnew(RXN(i, j, k)) times their
corresponding costs (Cfeed(RXN(i, j, k)) and Caux(RXN(i, j, k)),
respectively) in dollars per kilogram, as presented in eq 22.
The raw materials, intermediate chemicals, and catalyst costs
are presented in Table S1. For the catalyst costs, the catalyst
loading and lifetime were considered in the calculations. In
Table S4, the liquid hourly space velocity (LHSV), the weight
hourly space velocity (WHSV), and the gas hourly space
velocity (GHSV) values as well as catalyst lifetimes considered
for the catalyst cost calculations are presented
(
C RM = mfeedstock(RXN(i , j , k))·Cfeed(RXN(i , j , k))
+ ∑ mnew(RXN(i ,j ,k))·Caux(RXN(i ,j ,k)))·OY (22)
4.3. MINLP Algorithm Implementation. The proposed
MINLP model has the advantage to find the optimal network
flowsheet that fits a given set of constraints. Therefore, if the
set of constraints is changed, the problem solution might
change also. In this section, first, the optimization constraints
belonging to a feasible region, which need to be set to define
the limits of performance for the system, are described.
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Likewise, the major decisions taken by the algorithm according
to the constraints are presented. Then, to prove the flexibility
of the optimization algorithm, three different case studies were
evaluated. The case studies consider different values for the
feedstock and product flow rates.
4.3.1. Constraints for Optimization Solution. Based on the
input information, the optimization algorithm evaluates the
superstructure and selects the optimal technology within a set
of technological selection constraints, mass balance constraints,
and techno-economic evaluation constraints. For the MINLP
algorithm implementation, boundaries and initial values for the
following variables should be given as follows:
• Feedstock mass flow rate and composition.
• Gasoline minimum or maximum desired flow rate
(based on the rigorous simulation results).
• Diesel minimum or maximum desired flow rate (based
on the rigorous simulation results).
• Product component maximum flow rate (based on the
rigorous simulation results).
• Integer variable values: existence (1) or absence (0) of
integration possibilities.
• Fractional variable values: fraction of products being
sent to upgrading units.
After the definition of the initial values and the
implementation of the algorithm, the major decisions taken
by the algorithm are as follows:
• Feedstock mass flow rate and composition (in case
different sources are considered).
• Processing block interconnection.
• NCG integration.
• Water integration.
• Cogeneration.
• Fraction of gases and/or water sent to cogeneration for
steam and/or electricity production.
• Fraction of syngas or pyrolysis oil being sent to the
upgrading alternatives.
• Final product flow rates.
Some of these decision variables, but not all, are restricted to
be integer. For instance, the integration decision variables are
restricted to be integer. For this, a branch-and-bound approach
was selected since it is recommended to solve problems in
which some of the variables are constrained to be integer.
Branch-and-bound strategy considers the division of the
feasible region into more manageable subdivisions. The
subdivisions are generated solely by the integer variables.
The general procedure is to subdivide based upon the variable
with the highest objective contribution.17 In this study, it was
subdivided in terms of the possible mass and energy
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integrations. To achieve this, the model uses as a solver,
branch-and-reduce optimization navigator (BARON), which is
recommended for the global solution of nonlinear program-
ming (NLP) and MINLP. Moreover, BARON implements
deterministic global optimization algorithms of the branch-
and-bound type that are guaranteed to provide the global
optima under fairly general assumptions.18
On the other hand, the selection of processing blocks
conforming the optimal technological route was performed by
not specifying the block interconnections as integer variables
but as fractional variables (i.e., stream splitting and mass
distribution), and therefore, the model can consider all the
process routes simultaneously.
4.4. MINLP Algorithm Solution. To find the optimal
route for each case study, the algorithm considers a set of
initial values for the feedstock flow rate, feedstock composition,
types of integrations, fraction of thermochemical products sent
to the different upgrading alternatives, and the maximum and/
or minimum biofuel-desired flow rates, as presented in Figure
4. Boundaries concerning gasoline and diesel production were
given based on the actual component flow rates taken from the
rigorous simulations. For instance, the minimum diesel flow
rate obtained from the simulation of the base case processes
was around 50 kg/h and the maximum flow rate was 343 kg/h.
On the other hand, for the gasoline production, the minimum
flow rate was 260 kg/h and the maximum was 830 kg/h. Based
on the data collected, initial values were given, which are the
starting point that allows the algorithm to search the optimal
solution within the limits and product profile specifications.
The MINLP problem was solved on an HP EliteBook laptop
with Intel(R) Core(TM) i5-6300U, 240 GHz CPU, 8 GB
RAM, and Windows 10 64-bit. The final solution was
determined by analyzing which reaction and separation blocks
present inlet flow rates (min(RXN(i, j, k)) and min(SEP(i, j, k)),
respectively) and by confirming if there is consistency between
the components produced from the reaction blocks and
reported final fuel product mass component flow rate.
Moreover, to determine the possible integrations, the Xn
resulting values were analyzed and collected. Likewise, to
quantify the fraction of syngas or pyrolysis oil being sent to the
different upgrading alternatives, the Ynvalues were collected.
To demonstrate the methodology for the optimal synthesis
of network process flowsheets for different scenarios of product
and process specifications, three different case studies
considering different fuel product profiles and constraints
were considered, as will be described in the next section.
5. CASE STUDIES FOR SUPERSTRUCTURE MINLP
ALGORITHM IMPLEMENTATION AND SOLUTION
5.1. Case Study 1: Maximization of Gasoline and
Diesel Fuel Production. The objective of the first case study
is to generate a process route that can promote the
simultaneous production of gasoline and diesel and minimize
the TCOM. For this case study, as initial values, the feedstock
flow rate going to the pyrolysis section was initially set to 250
kg/h; likewise, the feedstock flow rate going to the gasification
section was set to 250 kg/h. These initial values are given to
guarantee that both processes are considered in the
optimization solving. Concerning the feedstock composition,
as the starting point, both feedstock streams contain 50 wt %
spruce and 50 wt % pine. Additionally, the initial values for the
integer variables that define the mass and energy integrations
were set as 1, so the optimization can consider initially all
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integration possibilities. Concerning the biofuel-desired flow
rates, gasoline and diesel flow rates were set to be greater than
or equal to 260 and 50 kg/h, respectively. These values were
given according to the minimum gasoline and diesel flow rates
obtained from the simulations and are given in section 4.4.
For this case, the optimization solution proposed the
processing blocks depicted in Table 2. The results proposed
Table 2. MINLP Solution: Processing Blocks for Case Study
1
processing
block description products
RXN(6,2) thermochemical conversion: syngas
Gasification
RXN(2,2) combustion CO2
RXN(7,2) LTFT distillate and
wax range
RXN(9,2) HTFT naphtha range
and gases
RXN(10,2) fractional upgrading: cat. reforming and gasoline and
alkylation gases
RXN(8,2) distillate hydrogenation diesel
RXN(13,2)/ wax hydrocracking gasoline and
(14,2) diesel
SEP(6,3) separation of gases and gasoline
SEP(7,3) separation of syngas and impurities
SEP(8,3) separation of FT syncrude fractions
SEP(11,3) fractionation column for final fuels
recovery
a combined flowsheet of gasification followed by simultaneous
high- and low-temperature FT (HTFT and LTFT, respec-
tively) reactions and FT fractional upgrading blocks (distillate
hydrotreating, wax hydrocracking, naphtha hydrotreating and
reforming, and tail gas alkylation) as the global optimal
technological route. This route was designated as combined
alternative one (CA1-GLTHT), and it is presented in Figure 5.
As can be observed from Table 2, the fuel components
produced from each reaction block are consistent with the
desired fuel targets. Likewise, from Figure 5, it can be observed
that the waste gases from the lumped-block RXN(10,2)-
SEP(8,3) that could produce more gasoline products were not
upgraded, confirming that the gasoline production is not the
only objective for this case study. Concerning the other
decision variables, a feedstock composition of 50 wt % spruce
and 50 wt % pine to be sent to the gasification section was
proposed, which is understandable since spruce and pine
present similar cost and composition. Moreover, by analyzing
the optimization solution, values for both fractional variables
Y3 and Y4 were of 0.5, which means that the LTFT
(RXN(7,2)) and HTFT (RXN(9,2)) have the same flow
rate, as presented in Table S5. The values of the resulting
integration decision variable Xn are also reported in Table S5.
Concerning the possible mass and energy integrations, from
Table S5, is possible to observe that if the objective is to
increase the production of biofuels and minimize the TCOM,
then steam and electricity generation in the cogeneration plant
should be considered. The capital cost, energy cost, operating
labor cost, raw material costs, waste streams cost, TCOM, and
productivity of the proposed route with and without the
integration will be presented and compared with the base case
processes in section 6.
5.2. Case Study 2: Maximization of Gasoline Fuel
Production. In this case study, the production of gasoline is
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Figure 5. Global optimal solution CA1-GLTHT for case study 1.
Figure 6. Global optimal solution CA2-GLTHT for case study 2.
preferred, and thus, the diesel flow rate was set to be lower
than or equal to 200 kg/h, and the gasoline flow rate was set to
be greater than or equal to 500 kg/h. These values are given
according to the biofuel flow rates obtained from the
simulations. For instance, the diesel production for most of
the base case processes is around 200−343 kg/h, and the
gasoline production is around 523−830 kg/h. Therefore,
values between these ranges were given as the maximum diesel
and minimum gasoline flow rates. On the other hand, the
initial values for the feedstock flow rate, feedstock composition,
and integer variables (integrations) were the same given as in
case study 1.
For this case study, the MINLP optimization solution was
designated as CA2-GLTHT and is presented in Figure 6. As
can be observed, this process route is a combined flowsheet of
Gasification followed by simultaneous high- and low-temper-
ature FT reactions and fractional upgrading units, as obtained
for case study 1. Likewise, the same feedstock flow rates,
compositions and fractions of syngas sent to the HTFT and
LTFT, were obtained by the MINLP solution. However, the
fractional upgrading units needed are different from the
optimal solution for case study 1; because in this case study,
the production of gasoline is preferred, and the diesel
production is not a priority. Therefore, in this case, tail gas
alkylation and naphtha reforming (RXN(10,2)), LPG
oligomerization (RXN(12,2)), and wax hydrocracking units
(RXN(13,2)/RXN(14,2)) are required in which most of the
components are upgraded to gasoline blends. From Figure 6, it
can be observed that there is no waste gases from the lumped-
block RXN(10,2)-SEP(8,3) since the gases are being upgraded
to gasoline components via alkylation and oligomerization.
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Regarding the decision values of the integration variables,
steam and electricity generation in the cogeneration plant is
considered similarly as in case study 1. Except that in this
scenario, the electricity generated might be lower, given that
most of the gases are upgraded to gasoline components and
there is a low amount of waste gases available for power
generation.
The detailed numerical comparison between the CA2-
GLTHT optimal process route and base case processes is
presented in section 6.
5.3. Case Study 3: Maximization of Diesel Fuel
Production. Contrary to the previous case, in this case
study, the production of diesel fuel is preferred, and thus, the
gasoline flow rate was set to be lower than or equal to 200 kg/
h, and the diesel flow rate was set to be greater than or equal to
300 kg/h. The limits for the biofuels flow rates were given
based on the minimum gasoline and maximum diesel flow rates
obtained from the base case process simulations and as
presented in section 4.4. Moreover, the same initial values for
the feedstock flow rate, feedstock compositions, and integer
variables were given as in the previous cases.
The MINLP solution proposed, as well as in the other two
case studies, a combined flowsheet of gasification followed by
simultaneous HTFT and LTFT reactions and fractional
upgrading units as the global optimal technological route.
However, in this process route, the values obtained for the
fractional variables Yn were different. For instance, only 20% of
the syngas product should be sent to HTFT and 80% to LTFT,
which is understandable since LTFT produces more long chain
hydrocarbons to be upgraded to diesel. This process route was
designated as CA3-GLTHT and is presented in Figure 7. As
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Figure 7. Global optimal solution CA3-GLTHT for case study 3.
Figure 8. CA1-GLTHT process flowsheet for simulation and evaluation.
Figure 9. CA2-GLTHT process flowsheet for simulation and evaluation.
can be observed, since the production of diesel is preferred, the
fractional upgrading units required are olefin alkylation,
naphtha hydrotreating and reforming (RXN(10,2)), distillate
hydrogenation (RXN(8,2)), and wax hydrocracking (RXN-
(13,2),(14,2)), which are the same units as in the first case.
The main differences between this case study and the previous
cases are the amount of syngas being sent to each
corresponding FT reactor, and that the alkyl benzenes
produced are mixed with the diesel components instead of
being mixed with all the upgraded streams, which allows
reducing the cetane number and increases the diesel density.
On the other hand, the decision values of the integer variables
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were the same as in the other two cases, and thus, the gases
and wastewater were sent to the cogeneration plant.
The detailed numerical comparison between the CA3-
GLTHT optimal process route and base case processes is
presented in section 6.
6. OPTIMAL SCENARIO RIGOROUS SIMULATION
AND EVALUATION
The main task of the MINLP optimization algorithm is to
synthesize the optimal network flowsheet. Therefore, given the
product profile specifications and constraints, the MINLP
optimization algorithm searches all the possible networks from
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Figure 10. CA3-GLTHT process flowsheet for simulation and evaluation.

Table 3. Comparison of the Three Optimization Processes with the Base Case Processes
parameter BC-PHS BC-PCCF BC-GHTUF BC-GLTUF BC-GHTH CA1-GLTHT CA2-GLTHT CA3-GLTHT
upgraded prod. (kg/h) 942 902 818 700 985 1022 1069 1030
total fuel prod. wt % 78 60 70 87 89 90 97 45
gasoline wt % 54 45 64 38 84 69 80 10
diesel wt % 24 15 6 49 5 21 17 35
CCtot($/year) 473,509 205,791 107,409 82,834 123,445 88,412 88,652 95,115
COL($/year) 1,621,120 1,215,840 1,621,120 1,621,120 1,621,120 1,621,120 1,621,120 1,621,120
CRM($/year) 17,653,109 5,712,142 5,977,087 4,680,232 7,989,420 6,934,368 7,313,331 3,955,324
ECtot($/year) 357,069 131,666 1,359,842 152,704 1,401,245 235,434 229,412 122,105
CWT($/year) 6,344,611 6,541,891 4,612,630 4,289,046 4,583,126 4,484,208 4,371,508 4,456,510
TCOM($/year) 34,514,631 18,611,274 19,153,691 15,668,889 21,647,985 18,784,844 19,105,008 14,949,035
TCOM w/int. ($/year) 34,114,491 18,262,395 17,619,701 15,341,811 20,949,776 18,274,260 18,766,123 14,680,510
productivity (GGE/year) 2,742,610 2,133,829 1,590,358 1,903,308 2,202,228 2,416,304 3,586,161 1,800,690
TCOMGGE($/GGE) 12.4 8.5 11.1 8.1 9.5 7.5 5.2 8.1

the superstructure including possible mass and energy
integrations and gives the optimal process flowsheet that
meets the objective function, product profiles, and constraints.
Moreover, to interpret the model predictions correctly, it is
desirable to quantify the prediction uncertainty. Therefore,
from the obtained MINLP optimal network, final rigorous
design, simulation, and evaluation of the process flowsheet
with the Aspen process simulator should be carried out. The
results from the rigorous simulation allow the consistent
numerical comparison between the optimal solutions and base
cases. Likewise, the GAMS solution and results from the
rigorous simulation can be compared and the prediction of the
uncertainty and modelling error can be quantified. Moreover,
the final objective of the rigorous simulation is to finalize the
parameter designs for the obtained optimal flowsheet from the
optimization algorithm, which serves as to reconcile the blocks
and stream information for the obtained process flowsheet.
6.1. Process Flowsheet Setups for Simulation and
Evaluation with the Process Simulator. From the MINLP
solutions, three corresponding process flowsheets were
designed for the evaluation and simulation of the CA1-
GLTHT, CA2-GLTHT, and CA3-GLTHT network process
routes, as presented in Figures 8, 9, and 10, respectively. The
rigorous simulations were performed in Aspen Plus V8.8 using
as starting points the setups and designs of the gasification-
based process routes introduced in part 1 of this study and
evaluated by Ibarra-Gonzalez and Rong.14 Then, because of
changes in the composition and flow rates of the FT fractions,
as well as the upgrading units required, minor adjustments
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were done to the design parameters to achieve the desired
conversions and recoveries. For the rigorous simulation of the
proposed process routes and cogeneration plant, the selection
of the thermodynamic model for each block has been selected
according to the stream composition. The thermodynamic
package Soave−Redlich−Kwong equation of state with
Kabadi−Danner mixing rules was selected due to its
recommended application for mixtures containing water and
hydrocarbons.19 In addition, the electrolyte and non-electro-
lyte NRTL models with Redlich−Kwong equation of state
were employed for the separation units. For instance, when the
stream contains ammonia, water, and some gases dissolved that
were carried over from the Scrubber, the Electrolyte NRTL
model was selected because is suited for solutions with
multiple solvents, and dissolved gases, and it is very suitable for
any low-to-moderate pressure applications.19
From the simulations, product profiles, product properties,
waste streams flow rates, and auxiliary stream flow rates were
collected. Aspen process economic analyzer V8.8 was used to
calculate energy and equipment costs for the process routes
with and without the recommended mass and energy
integrations. The numerical evaluation was used to compare
the new process routes with the initial five base case process
routes introduced in Part 1 of this study. The data and
information obtained throughout process setups and rigorous
simulations ensure that the evaluation, comparison, and
analysis of the different process route performance is within
the same framework and platform.
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6.2. BtL Process Routes Comparison. The numerical
comparison between the new and base case process routes was
performed considering the total upgraded product flow rate,
product profiles, economic evaluation, and annual productivity.
For the economic evaluation and comparison, the results from
the rigorous simulations, the prices presented in Table S1, the
equations presented in section 4.2 (capital cost (eq 16), energy
costs (eqs 17 and 18), operating labor costs (eq 19), wastes
disposal costs (eq 21), raw material costs (eq 22), and
TCOMGGE (eq 1)) were employed together with the TCOM
calculation depicted in eq 23. For the implementation of these
equations, feedstock flow rates, auxiliary reagent flow rates,
emission streams, capital costs, and energy costs were collected
from the rigorous simulations. On the other hand, component
market prices, average operator salary, and costs of hazardous
and non-hazardous waste components were collected from
literature.15,16
TCOM = 0.280CCtot + 2.73COL + 1.23(ECtot + C WT
+ C RM) (23)
In Table 3, the economic results of all the process routes
were collected including capital costs, energy costs, operating
labor costs, waste disposal stream and raw material costs, and
TCOM considering 8000 h of annual operation. Likewise, for
comparison purposes, the upgraded product flow rate, product
profiles, the TCOM of the process routes considering heat and
power integration, the productivity, and the fuel product value
per GGE (TCOMGGE) are reported. In Figure 11, the
contribution of the different costs (dollars per GGE) in the
Figure 11. Cost contribution in the TCOMGGE($/GGE) for the base
cases and three optimization case processes.
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TCOMGGE is presented. The fuel product profiles and
properties for each process route were calculated from the
rigorous simulations and are presented in Figure 12 and Table
4, respectively.
Figure 12. Product profiles of the BtL process route base cases and
three optimization cases.
Moreover, the prediction of the uncertainty of the MINLP
model was performed by comparing the results obtained from
the optimization in GAMS with the results from the rigorous
simulations, as depicted in Table 5. To calculate the
uncertainty of the model, the mass outlet flowrate of the
components produced from the algorithm implementation and
the total mass outlet flowrates of the gasoline and diesel
produced from the rigorous simulation of the process
configuration generated by the optimization were presented.
From the numerical results, it was demonstrated that when
simultaneous production of gasoline and diesel is preferred, the
CA1-GLTHT is the optimal technological route, producing
considerable amounts of both diesel and gasoline at lower
TCOM per GGE. For instance, the CA1-GLTHT could
produce 33% more biofuels (kilograms per hour) than BC-
GLTUF and 20% more than BC-PHS, and it presented a
gasoline equivalent cost of $7.5/GGE, which is $0.6/GGE
cheaper than the biofuels produced from BC-GLTUF. On the
other hand, if gasoline production is desired, the CA2-GLTHT
is the optimal process route since it can increase the gasoline
production by 4% compared to BC-GHTH and the TCOM is
$4.3/GGE cheaper. The detailed stream table for CA2-
GLTHT is presented in Table S6. Finally, if diesel production
is desired, the CA3-GLTHT is the optimal process route since
diesel production can be increased by 5% compared to BC-
GLTUF and the TCOM considering heat and power
integration is 4.4% lower. Moreover, even though BC-
GLTUF presents a higher productivity of total biofuels, if
diesel production is preferred, the CA3-GLTHT is the optimal
route since it only focuses on its production and also improves
the diesel properties. For instance, the cetane number was
reduced and the HHV and density were increased and can be
observed in Table 4. Likewise, as can be observed, the TCOMs
of CA1-GLTHT and CA2-GLTHT are higher compared to
BC-GLTUF, BC-GHTUF, and BC-PCCF. This is due to the
fact that, in the combined alternatives, the upgrading block
configurations allow the upgrading of the majority of the
products into fuels, and therefore, more auxiliary reagents are
needed to achieve the conversions, which leads to an increase
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Table 5. Product Flow Rate Comparison between GAMS

1.08
diesel

38.6
CA3-GLTHT
and Aspen Plus Simulation Results for the Three

804

54
Optimization Cases
GAMS Aspen Plus difference between
gasoline

46.33

1.04
flow rate flow rate modeling

85
691
case studies fuel (kg/h) (kg/h) approaches %
CA1-GLTHT gasoline 755 705 7.09
diesel 217.3 215 1.07
1.21
diesel

37.7

CA2-GLTHT gasoline 839 848 1.06

CA2-GLTHT

802

59

diesel 199 184.6 7.80

CA3-GLTHT gasoline 100 103 2.91
gasoline

1.09

diesel 385.2 360.5 6.84

43.5
842

101

in the energy and raw material costs. On the other hand, by

1.09
diesel

37.3

upgrading the majority of the products, the productivity

CA1-GLTHT

802

58

increases leading to lower TCOM per GGE.

Concerning the fuel product value per GGE, the CA2-
gasoline

GLTHT is the optimal process route among all the process

0.89
43.22
848

100

routes evaluated in this study. It presented the highest biofuel

production and lowest product value of $5.2/GGE if heat and
power integrations are considered. However, compared to the
38.95

1.06
diesel

commercial gasoline price of $2.54/gallon reported for USA,20

753

77
BC-GHTH

the fuel product values per GGE obtained for all the process
routes explored are higher, which is expected for pioneer plants
during the first several years of operation. For instance, a study
gasoline

44.60

0.87

performed by researchers from the National Renewable Energy

803

88

Laboratory (NREL) stated that for a first of its kind plant, such
Table 4. Advanced Biofuel Properties for the Base Case and Three Optimization Case Processes

as high-temperature and low-temperature pioneer plants, the

1.28
diesel

fuel product values are estimated to be $7.60/GGE and $8.10/

771
34
82
BC-GLTUF

GGE, respectively.21
To further increase the commercial application of these
technologies, other aspects including the raw material
gasoline

44.52

0.96

availability, location, plant capacity, conversion steps for total

787

78

production processes, desired products and relevant by-

products, transportation costs as well as the state of technical
38.14

1.15
diesel

development, overall production costs, and government

72
760
BC-GHTUF

policies need to be considered. For instance, if the processing

plant is considered to be in Denmark where the cost of
gasoline is $6.22/Gallon20 and sufficient raw material can be
gasoline

44.25

0.91

available, then the feasibility increases.

816

104

Furthermore, the differences between the values obtained in

GAMS and Aspen are due to the fact that in the material
0.99

balances where the conversion factors are introduced (eqs 4

diesel

34
13
1091

and 7), the conversions are calculated according to the flow of

BC-PCCF

the limiting reagent.

gasoline

45.35

0.91

7. CONCLUSIONS
811

93

In this work, the softwood BtL superstructure, proposed in

Part 1 of this work, with the technical and economic data and
information prepared for its units and blocks, has been
45.83

1.11
diesel
706.5

42

developed into an MINLP optimization algorithm. The

BC-PHS

defined MINLP problem sets the objective to minimize the

TCOM of BtL fuels under different cases and integration
gasoline

46.83

0.97
738.1

scenarios. The superstructure was coded in GAMS 24.5.6, and

60

the solver BARON 14.4 was employed to determine the

process route that meets the objective function. From the
mathematical modeling of the superstructure and its
avg. octane value
density (kg/m3)
HHV (MJ/kg)
cetane number

implementation, optimal technological routes for the produc-

properties

tion of gasoline and diesel considering different product

profiles and integration possibilities were generated.
GGE

To evaluate the algorithm, three cases with different product

specifications have been studied, which demonstrated that the
N https://dx.doi.org/10.1021/acs.iecr.0c02903
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

optimization methodology can generate optimal process routes BtL biomass to liquid
for the specified cases. From the process routes evaluated, it CA1-GLTHT combined alternative one
was found that the CA2-GLTHT is the optimal technological CA2-GLTHT combined alternative two
route for the production of advanced biofuels as gasoline and CA3-GLTHT combined alternative three
diesel. This process can increase the production of advanced Caux(RXN(i, j, k)) auxiliary stream costs
biofuels while reducing the TCOM when heat and power CCadj(i, j) processing block-adjusted capital cost
integrations are considered. The process can produce gasoline CCbase(i, j) processing block-base capital cost
and diesel with similar fuel properties to petroleum fuels and CCtot total capital cost
with a fuel product price as of $5.2/GGE. Cfeed feedstocks costs
The results demonstrated that the integrated methodology COL operating labor costs
with the superstructure-based optimization can synthesize convf conversion factor
optimal total BtL biofuel production processes compared to CRM raw materials cost
the previous base case processes. CWT waste disposal costs

■
*
ASSOCIATED CONTENT
sı Supporting Information
DC

EC(i, j)
hazardous or nonhazardous disposal costs
($/kg)
processing block energy cost
The Supporting Information is available free of charge at ECtot total energy cost
https://pubs.acs.org/doi/10.1021/acs.iecr.0c02903. FT Fischer−Tropsch
Detailed information regarding the softwood BtL GGE gasoline gallon equivalent
superstructure diagram, market prices for raw materials, GHG greenhouse gas
utilities, and intermediate chemicals as well as processing GHSV gas hourly space velocity
block performance parameters, catalyst information, GLTHT gasification followed by simultaneous high-
integer, and fractional variables for a case study, and and low-temperature FT reactions and frac-
detailed stream table of the optimal process route (PDF) tional upgrading units

■
HHV high heating value
HTFT high-temperature Fischer−Tropsch
AUTHOR INFORMATION LHSV liquid hourly space velocity
Corresponding Author LPG liquified petroleum gas
Ben-Guang Rong − Department of Chemical Engineering, LTFT low-temperature Fischer−Tropsch
Biotechnology and Environmental Technology, University of mbase base mass inlet flow rate
Southern Denmark, Odense M DK-5230, Denmark; mfeedstock feedstock mass flow rate
Department of Chemistry and Bioscience, Aalborg University, min(i, j, k) actual mass inlet flow rate
Esbjerg DK-6700, Denmark; orcid.org/0000-0001-8730- MINLP mixed Integer Nonlinear Programming
5058; Phone: +45 9940 7668; Email: bro@bio.aau.dk min(RXN(i, j, k)) reaction block total inlet flow
min(SEP(i, j, k)) separation block inlet flow rate
Author
min(WWD(i, j, k)) total waste stream flow rate
Paola Ibarra-Gonzalez − Department of Chemical Engineering, MJ megajoule
Biotechnology and Environmental Technology, University of mnew(RXN(i, j, k)) auxiliary stream flow rate
Southern Denmark, Odense M DK-5230, Denmark mout(RXN(i, j, k)) reaction block outlet flow rate
Complete contact information is available at: mout(SEP(i, j, k)) total separation block outlet flow rate
https://pubs.acs.org/10.1021/acs.iecr.0c02903 moutn(SEP(i, j, k)) separation block outlet stream flow rate
moutPB flow rate coming from a previous block
Notes mrec(SEP(i, j, k)) recycle stream
The authors declare no competing financial interest. NCGs noncondensable gases

■ ACKNOWLEDGMENTS
The authors acknowledge financial support from CONACYT-
Newf(RXN(i, j, k))
NLP
Nnp(i, j)
auxiliary component ratio
nonlinear programming
total number of unit operations included in
The Mexican National Council for Science and Technology each processing block
(grant 326204/439098) and the University of Southern NOL number of operators per shift
Denmark. NREL National Renewable Energy Laboratory

■
Avg
NOMENCLATURE
average
OL
OY
P
operating labor
operational year
number of processing steps involving handling
BARON branch-and-reduce optimization navigator of solids
BC base case prod product
BC-GHTH gasification-HTFT hydrocarbon production- RXN reaction block
FT hydrocarbon hydroprocessing SEP separation block
BC-GHTUF gasification-HTFT hydrocarbon production- Sepf recovery factor
FT hydrocarbon upgrading-fractionation TCOM total cost of manufacturing
BC-GLTUF gasification-LTFT hydrocarbon production- TCOMGGE total cost of manufacturing per gasoline gallon
FT hydrocarbon upgrading-fractionation equivalent
BC-PCCF pyrolysis-catalytic cracking-fractionation w/int with integration
BC-PHS pyrolysis-hydroprocessing-separation WHSV weight hourly space velocity

O https://dx.doi.org/10.1021/acs.iecr.0c02903
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Xn integer variable (21) Swanson, R. M.; Satrio, J. A.; Brown, R. C.; Platon, A.; Hsu, D.
fractional variable, fraction of product sent to D. Techno-Economic Analysis of Biofuels Production Based on Gas-
Yn upgrading units ification; NREL, 2010.

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