processes
Article
Renewable Fuels from Integrated Power- and Biomass-to-X
Processes: A Superstructure Optimization Study
Philipp Kenkel 1,2, * , Timo Wassermann 1,2
Citation: Kenkel, P.; Wassermann, T.;
Zondervan, E. Renewable Fuels from
Integrated Power- and Biomass-to-X
Processes: A Superstructure
Optimization Study. Processes 2022,
10, 1298. https://doi.org/10.3390/
pr10071298
Academic Editor: Alberto J. Moya
Received: 30 May 2022
Accepted: 27 June 2022
Published: 30 June 2022
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations.
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Processes 2022, 10, 1298. https://doi.org/10.3390/pr10071298
and Edwin Zondervan 3
1 Artec Sustainability Research Center, University of Bremen, Enrique-Schmidt-Straße 7,
28359 Bremen, Germany; timo.wassermann@uni-bremen.de
2 Advanced Energy Systems Institute, University of Bremen, Enrique-Schmidt Straße 7,
28359 Bremen, Germany
3 SPT-PSE, University of Twente, 7522NB Enschede, The Netherlands; e.zondervan@utwente.nl
* Correspondence: kenkel@uni-bremen.de
Abstract: This work presents a superstructure optimization study for the production of renewable
fuels with a focus on jet fuel. Power-to-X via the methanol (MTJ) and Fischer–Tropsch (FT) route
is combined with Biomass-to-X (BtX) via an algae-based biorefinery to an integrated Power- and
Biomass-to-X (PBtX) process. Possible integration by algae remnant utilization for H2 /CO2 produc-
tion, wastewater recycling and heat integration is included. Modeling is performed using the novel
Open sUperstrucTure moDeling and OptimizatiOn fRamework (OUTDOOR). Novel methods to
account for advanced mass balances and uncertain input data are included. Economic optimization
proposes a PBtX process. This process combines algae processing with MTJ and depicts a highly
mass- and energy integrated plant. It produces fuels at 211 EUR/MWhLHV (ca. 2530 EUR/t), a cost
reduction of 21% to 11.5% compared to stand-alone electricity- or bio-based production at algae costs
of 25 EUR/tAlgae-sludge and electricity costs of 72 EUR/MWh. Investigation of uncertain data indi-
cates that a combination of BtX and MTJ is economically superior to FT for a wide parameter range.
Only for high algae costs of >40 EUR/tAlgae-sludge stand-alone electricity-based MTJ is economically
superior and for high MTJ costs above 2000–2400 EUR/tJet FT is the optimal option.
Keywords: algae biorefinery; Power-to-X; superstructure optimization; renewable fuels; python
1. Introduction
Due to the urgent threat of climate change induced by anthropogenic greenhouse
gas (GHG) emissions, various countries have set out targets for an extensive reduction
in CO2 and other GHG. In some sectors such as electricity generation, the defossilization
is progressing fast in countries such as Germany, achieving shares of renewable energy
production of about 50% in 2020. However, other sectors such as the (petro)chemical
industry as well as the mobility sector are much harder to defossilize.
There are already a plethora of different renewable processes to produce petroleum
and petrochemical products such as jet fuel as diesel but also platform chemicals, such
as light olefins, aromatics or methanol. Bio-based processes (Biomass-to-X = BtX) such as
biorefineries utilize energy crops but also waste streams, lignocellulose materials and even
micro- and macro algae to produce fuels and biochemicals [1,2]. Electricity-based processes,
so-called Power-to-X (PtX) processes, apply water electrolysis in combination with carbon
capture to produce mixtures of hydrogen (H2 ) and carbon dioxide (CO2 ), that serve as
reacting agent in methanol or Fischer–Tropsch synthesis to produce hydrocarbons [3].
However, each process alternative has its own characteristics in terms of cost, utility
demands, efficiency or consumption of raw materials such as fresh water.
In order to find an optimal (sustainable) process design, the different concepts have
to be compared to each other under specific boundary conditions. What is more, not only
should stand-alone processes be reviewed, but also partly or totally integrated Power- and
https://www.mdpi.com/journal/processes
Processes 2022, 10, 1298 2 of 30

Biomass-to-X processes (PBtX) have to be considered, leading to a vast number of potential

process designs.
One way to investigate optimal process designs where many different process layouts
are available is the application of superstructure optimization. Superstructure optimization
is a methodology for process synthesis which utilizes mathematical models and optimiza-
tion algorithms to identify optimal process flowsheets for given objective functions [4]. A
superstructure represents a large number of possible flowsheets, where unit-operations are
described as generic blocks by mass, energy and cost balances [4,5]. Using mathematical
modeling, the unit-operations and possible flowsheets are translated into a mathematical
program which can be solved using state-of-the art optimization solvers [1,6].
Relevant work regarding superstructure optimization in the area of biorefinery process
design was carried out by Gong and You, Bertran et al., Galanopoulos et al., Niziolek et al.
and Onel et al. Gong et al. utilized superstructure optimization to identify cost- and emis-
sion optimal algae biorefineries producing biodiesel, green diesel and other value-added
products [7]. They concluded that manufacturing algal bioproducts reduces GHG by 63%
compared to the petrochemical counterparts. Combining biodiesel production with value-
added products also reduces the costs of the biodiesel to the level of cost-competitiveness to
other biodiesel products. Galanopoulos et al. combined a biorefinery based on wheat-straw
for the production of bioethanol and levulinic acid with an algae-based biorefinery for
biodiesel and glycerol production. The integration of wastewater and CO2 from wheat-
straw refinery as a raw material in algae cultivation and the recycling of algae remnant as a
raw material for bioethanol production results in a cost reduction of about 40% for open
pond cultivation [8]. Niziolek et al. investigated the bio-based production of aromatics via
methanol amongst others. Their superstructure includes biomass gasification, methanol
synthesis, methanol-to-aromatics and several recycling schemes for light gases such as
combustion for energy production or conversion in autothermal reforming. Different
biomass feedstocks are studied, namely corn stover, switchgrass and hardwood. They
calculate payback times of roughly 9 years for the most profitable process configuration.
Onel et al. set up a superstructure using forest residues and natural gas to produce liquid
transportation fuels and olefins by utilizing the Fischer–Tropsch route [9]. They also incor-
porated heat, power and water integration in their model. They concluded that the optimal
process configuration depends on the desired fuels and olefins and that such a combined
production could lead to economic viability [9].
In the field of PtX superstructure optimization work has been performed by Sanchez
et al., Uebbing et al. and Kenkel et al. [10–12]. Sánchez et al. investigated a superstructure
of ammonia-based electricity production. In their problem, decisions on gas clean-up after
electricity production in a combined gas and steam turbine as well as final N2 /Air sepa-
ration are made. The MINLP uses detailed sub-models for, e.g., ammonia decomposition
and aims to minimize operation costs of power production. Results show that power
production costs can vary between 0.05 and 0.81 EUR/kWh depending on plant capacity
and ammonia price [10]. Uebbing et al. investigated a CO2 methanation superstructure
combining biogas processing and water electrolysis to provide synthetic natural gas for
the gas grid. They combine detailed unit models with indirect heat integration and op-
timized for maximal exergetic efficiency and minimal capital costs. Results show that
using solid oxide electrolysis for H2 supply has a higher exergetic efficiency than using
alkaline electrolysis [11]. However, this comes at the price of substantial higher capital costs.
Kenkel et al. investigated bi-criteria power-to-methanol process designs with different
CO2 sources and different electrolyzer types in combination with direct hydrogenation
of CO2 to methanol [12]. In their work, green methanol is produced cost-optimally by a
combination of low-pressure alkaline electrolysis, CO2 from flue gases captured by amine
scrubbing and utilization of purge gases for steam production. Using this process layout
methanol is produced at ca. 900 EUR/t, with H2 supply contributing over 70% of the total
costs [12].
Processes 2022, 10, 1298 3 of 30

In addition to superstructure-based studies, several conventional techno-economic

studies on the production of liquid fuels have been performed by Schemme et al., Liebner
et al., Albrecht et al. and König et al. among others [3,13–15]. Schemme et al. investigated
costs of several H2 process routes for fuels such as gasoline, diesel and DME. They con-
clude that DME is the cheapest option with ca. 1.85 EUR/lDiesel equivalent [14]. Liebner et al.
compare their MtSynFuels process with the Fischer–Tropsch route for the production of
fuels and calculate production of roughly 180 $/t using natural gas as raw material [14].
Albrecht et al. propose a standardized method for techno-economic evaluation of alter-
native fuels and demonstrate it on a combined Power-and Biomass-to-X process using
the Fischer–Tropsch route including PEM electrolysis and biomass pyrolysis among other
technology steps. They estimate fuel production costs in the range of 1.2–2.8 EUR/l [3].
König modeled a Fischer–Tropsch process for the production of jet fuel and calculated costs
at 3.38 EUR/kg [15].
While PtX as well as BtX and even PBtX processes a have been investigated, no
superstructure optimization has been performed to find optimal integrated PBtX process
designs for the production of jet fuel as one major mid- to long term required liquid fuel in
the transport sector. To close this knowledge gap, we present a superstructure optimization
study, which aims to find cost optimal process designs from an integrated PBtX jet fuel
refinery. This renewable refinery combines HEFA (hydroprocessed esters and fatty acids)
production from microalgae as well as remnant biogas processing together with water
electrolysis, carbon capture and thermochemical conversion of H2 /CO2 to jet fuel via the
methanol (methanol-to-jet = MTJ) or Fischer–Tropsch (FT) route. Such a comprehensive
superstructure has not been investigated in literature yet, and the deep integration of PtX
and BtX processes, including novel technologies with uncertain data requires an advanced
modeling approach as well as methodologies to handle the emerging uncertainties. In the
course of this study, the Open sUperstrucTure moDeling and OptimizatiOn fRamework
(OUTDOOR), a python-based superstructure modeling and optimization tool is enhanced
to facilitate such complex investigations.
This paper is structured as follows: First, the superstructure of the integrated refinery is
described in detail (Section 2), then the problem statement and solution approach are given
(Section 3). Section 4 presents the results of the process synthesis and gives a discussion on
the cost efficiency of novel processes as well as integrated concepts. Finally, a conclusion is
presented and further investigation is proposed.

2. Process Description
The general layout of the superstructure is depicted in Figure 1. It includes 11 main
processing steps. The bio-based pathway includes a biorefinery using algae biomass
as raw material to produce HEFA as main product, with minor shares of gasoline and
diesel as by-products. The PtX pathway includes different water electrolysis and carbon
capture technologies to produce H2 and CO2 with subsequent methanol or Fischer–Tropsch
synthesis, including their respective upgrading to jet fuel and further by-products. A
combined PBtX process is realized by integrating algae residue conversion to SynFeed
(H2 /CO2 mixture) as input for thermochemical synthesis as well as combined wastewater
management, purge gas utilization and heat integration. The detailed processing steps
and considered technology options of the renewable refinery are described in detail in the
following section.

2.1. Power-to-X Process

Electricity-based fuel production uses carbon capture processes for pure CO2 production
as well as water electrolysis for H2 production with oxygen (O2 ) by-product. H2 and CO2
are consumed in thermochemical synthesis by either methanol synthesis or Fischer–Tropsch
synthesis. Produced intermediates are afterwards upgraded depending on the primary
synthesis to liquid fuels.
Processes 2022,10,
Processes2022, 10,1298
x FOR PEER REVIEW 44 of
of3034

Bio-oils
Wet algae Algae Algae Algae oil
Lipid Extraction Liquid fuels
pretreatment upgrading

Residue

Algae residue
Waste water Fertilizer
treatment

Biogas Heat/
Purge gas
Biogas Electricity
utilization
Air / H2O / O2 Biogas Liquid
utilization bio-methane

SynFeed (H2/CO2)
Hydrogen

Purge

Flue gases/
Air Carbon Capture Carbon dioxide Methanol /
Thermochemical Fischer-Tropsch-crude Product Liquid fuels
synthesis upgrading
Hydrogen Waste water
H2 O Electrolysis
Oxygen

Waste water Recyle water/

treatment effluent

Figure1.1.Simplified
Figure Simplifiedrenewable
renewablerefinery
refineryrepresentation
representation(detailed
(detailedsuperstructure
superstructurerepresentation
representationwith
with
all unit-operations can be found in Appendix A, Table A1 and Figure
all unit-operations can be found in Appendix A, Table A1 and Figure A1). A1).

2.1. Power-to-X
2.1.1. Process
Carbon Capture
The carbon capture
Electricity-based section
fuel provides
production CO
uses 2 as a capture
carbon raw material for thermochemical
processes syn-
for pure CO2 produc-
thesis.
tion asThree different
well as technologies,
water electrolysis fornamely low temperature
H2 production direct(Oair
with oxygen capture (LT-DAC),
2) by-product. H2 and
oxyfuel
CO2 arefired cementin
consumed factory with subsequent
thermochemical cooling
synthesis and water
by either separation
methanol (OXY)
synthesis as well
or Fischer–
asTropsch
oil refinery flue gas scrubbing using monoethanolamine (MEA-CC) are
synthesis. Produced intermediates are afterwards upgraded depending on the included in
the superstructure [16–18]. While
primary synthesis to liquid fuels. LT-DAC and MEA-CC produce low-pressure CO 2 at
1 bar, OXY internally prepares the carbon dioxide at 70 bar. As shown in Figure 2 the low-
Processes 2022, 10,pressure
x 2.1.1. CO2 streams
Carbon
FOR PEER REVIEW Captureare mixed with potential flows from a CO2 -distributor5 (CO of 34 -DIST)
2
and compressed to high pressure for thermochemical synthesis.
The carbon capture section provides CO2 as a raw material for thermochemical syn-
thesis. Three different technologies, namely low temperature direct air capture (LT-DAC),
O2 from
- O2 -DIST
oxyfuel fired cement factory with subsequent cooling and water separation (OXY) as well
- O2 source
as oil refinery flue gas scrubbing using monoethanolamine (MEA-CC) are included in the
Flue gas
superstructure [16–18]. While LT-DAC and MEA-CC produce low-pressure CO2 at 1 bar,
CO2
OXYfactory
Cement internallyOXY prepares the 70 barcarbon dioxide at 70 bar. As shown in Figure 2 the low-pres-
sure CO2 streams are mixed with potential flows from a CO2-distributor (CO2-DIST) and
CO2 to
compressed to high Flue gaspressure for thermochemical synthesis.
- MeOH SYN
LT-DAC CO2-COMP - FT-M
Air CO2
1 bar
CO2 from CO2-DIST

Water to
H2O-DIST
Waste water to WWT

Flue gas

Refinery flue gas

Flue gas
CO2-DIST

MEA-CC
CO2 from
CO2 from VP
- ATR SEL
- TRIR SEL

Figure 2. Carbon capture process section of the superstructure.

Figure 2. Carbon capture process section of the superstructure.
2.1.2. Water Electrolysis
Water electrolysis provides the H2 feedstock for thermochemical synthesis as well as
hydrotreating processes. Included technologies are high- and low-pressure alkaline elec-
trolysis (HP-AEL/AEL) at 30 and 1 bar, high-pressure proton exchange membrane elec-
trolysis (HP-PEMEL) at 30 bar and solid oxide electrolysis (SOEL) at ambient pressure
(see Figure 3). While PEMEL and AEL operate at low temperatures of around 70 °C and
 Processes 2022, 10, 1298 5 of 30

2.1.2. Water Electrolysis

Water electrolysis provides the H2 feedstock for thermochemical synthesis as well
as hydrotreating processes. Included technologies are high- and low-pressure alkaline
Processes 2022, 10, x FOR PEER REVIEWelectrolysis (HP-AEL/AEL) at 30 and 1 bar, high-pressure proton exchange membrane 6 of 34
electrolysis (HP-PEMEL) at 30 bar and solid oxide electrolysis (SOEL) at ambient pressure
(see Figure 3). While PEMEL and AEL operate at low temperatures of around 70 ◦ C and
are powered solely by electricity, SOEL operates at elevated temperatures up to 1000 ◦ C
However, it is also used in the deoxygenation of bio-oil (BIO-U), hydrotreating of metha-
where part of the energy input is introduced as steam. Therefore, electricity demand
nol-to-jet
varies fromintermediates
4.4 kWh/Nm (MTJ) andkWh/Nm
3 to 4.9 Fischer–Tropsch crude
3 and capital hydrocracking
costs (FT-C). Addi-
from 700 EUR/kW el to
tionally, it can also[19–21].
3000 EUR/kW be usedItinisHEAT
assumedGEN andallELelectrolyzer
that GEN as well as sold as by-product
technologies achieve total(H2-
el
Pool). Emerging
conversion, O2 can
meaning either
that 1 kgbeof sold
waterasisby-product
converted to or0.112
usedkgin of
processes such kg
H2 and 0.888 as of
theOoxy-
2
fuel cement factory
(see Equation (1)). carbon capture and autothermal as well as tri-reforming of bio-me-
thane and biogas (further explained H2 O → in0.112
BtX process
H2 + 0.888sections).
O2 (1)

H2 to
- HEAT GEN
SOEL - EL GEN

H2- LH-COMP

Hydrogen
1 bar LP-H2-DIST
AEL

H2- LM-COMP
Process water
Hydrogen H2 70 bar
HP-AEL
30 bar to MeOH SYN
H2-MH-COMP

Hydrogen
MP-H2-DIST
HP-PEMEL 30 bar
H2 30 bar to FT-M

H2 30 bar to
- MTJ
Purified water from H2O-DIST
H2 from H2-PSA - HYDRO
H2 30 bar to BIO-U

H2 30 bar
- HEAT GEN
- EL GEN

H2 30 bar
to H2-Pool

O2 to O2-Pool

Oxygen O2 to OXY
O2-DIST
O2 to TRIR

O2 to ATR

Figure
Figure3.3.Water
Water electrolysis processsection
electrolysis process sectionofofthe
thesuperstructure.
superstructure.

2.1.3. Thermochemical
Three H2 compressors Synthesis and Upgrading
with different compression ratios are included in this super-
structure.
The thermochemical product synthesis is eitherHchosen
A first one compresses ambient-pressure 2 to methanol operating
as methanol pressure
synthesis or as
of 70 bar (H2 -LH-COMP) using multiple stages. A second compressor provides a single-
Fischer–Tropsch synthesis route (see Figure 4Error! Reference source not found.).
stage compression from 30 bar to 70 bar (H2 -MH-COMP) in order to connect HP-AEL and
Methanol synthesis is implemented as direct hydrogenation of CO2 at 70 bar and 250
HP-PEMEL to methanol synthesis. A third compressor depicts a single-stage compression
°C. It is modeled using a three-step surrogate process. This process includes the main
of ambient-pressure H2 to medium pressure of 30 bar (H2 -LM-COMP). High-pressure
methanol
hydrogenreactor
at 70 bar(MEOH
is solelySYN), a flash
used in evaporation
methanol synthesis.(MeOH
However,FLASH) to separate
medium- purge
(30 bar) and
gas of inert and unreacted components as well as a final distillation column (MeOH
low- (1 bar) pressure H2 has several applications in the process structure. Therefore, both DC)
which purifies the raw methanol by separating wastewater. Arising purge
streams are connected to their distinct distributing units MP- H2 -DIST and LP- H2 -DIST.gas is further
treated in the purge
Low-pressure H2 can gasbetreatment section,
distributed to the while wastewater
H2 -LM-COMP andisHprocessed
2 -LH-COMP in aaswastewater
well as
treatment
being usedplant (WWT).
in energy The surrogate
integration, where itmodel is basedwith
is combusted on other
a detailed
purgemodel provided
gases to produce by
Wassermann
either steam et al. with
(HEAT GEN)yield
or factors of the
electricity (ELmethanol reaction,to
GEN). In addition ascompression
given in Table 1. [18].
to 70 bar,
medium-pressure hydrogen is the electricity-based feed for Fischer–Tropsch synthesis.
Table 1. Yield factors of methanol reactor, derived from Wassermann et al. [18].

-- MeOH CO2 O2 H2O CO H2

Yield factor (wt.-%) 61.9 2.3 0.2 35 0.2 0.4
Processes 2022, 10, 1298 6 of 30

However, it is also used in the deoxygenation of bio-oil (BIO-U), hydrotreating of methanol-

to-jet intermediates (MTJ) and Fischer–Tropsch crude hydrocracking (FT-C). Additionally,
it can also be used in HEAT GEN and EL GEN as well as sold as by-product (H2 -Pool).
Emerging O2 can either be sold as by-product or used in processes such as the oxyfuel
cement factory carbon capture and autothermal as well as tri-reforming of bio-methane
and biogas (further explained in BtX process sections).

2.1.3. Thermochemical Synthesis and Upgrading

Processes 2022, 10, x FOR PEER REVIEW 8 of 34
The thermochemical product synthesis is either chosen as methanol synthesis or as
Fischer–Tropsch synthesis route (see Figure 4).

Purge gas to
- HEAT GEN
- EL GEN
SynFeed from H2 from MP-H2-DIST
SYNFEED COMP Crude methanol

MeOH FLASH MTJ

H2 from
- H2-LH-COMP Pure methanol
- H2-MH-COMP
Fuels (Jet fuel, Diesel,
MeOH DC Gasoline, LPG) to
Fuels-Pool
MeOH SYN

Waste water to WWT

Waste water to WWT

CO2 from
- CO2 -COMP FT-B
- OXY Fluegas

Fuelgas

Heat supply FT-R FT-DC

FT-Crude
FT-M
H2 from MP-H2 -DIST Fuels (Jet fuel, Diesel,
Gasoline, LPG) to
Fuels-Pool
RWGS Waxes
SynFeed from
- ATR-DIST Process water
- SMR-DIST Waste water to
- TRIR-DIST WWT

Purified water from WWT

H2 from
MP-H2-DIST
HYDRO

Figure 4. Thermochemical synthesis and upgrading process section of renewable refinery super-
Figure 4. Thermochemical synthesis and upgrading process section of renewable refinery superstructure.
structure.
Methanol synthesis is implemented as direct hydrogenation of CO2 at 70 bar and
2.2. ◦Biomass-to-X
250 Process
C. It is modeled using a three-step surrogate process. This process includes the main
The BtX
methanol process
reactor (MEOHpathway
SYN), is two-fold
a flash in this superstructure.
evaporation (MeOH FLASH)The first path
to separate utilizes
purge gas
biogas
of inert from a biogas plant
and unreacted with a as
components composition of 65
well as a final vol. -% CH
distillation 4 and (MeOH
column 35 vol. -%
DC)CO 2 for
which
the production
purifies the raw of SynFeedbyinseparating
methanol thermochemical synthesis.
wastewater. The
Arising second
purge gaspathway
is furtherdepicts
treated an
in
the purge gasbiorefinery
algae-based treatment section,
to producewhile wastewater is processed
hydroprocessed esters andinfatty
a wastewater treatment
acids (HEFA) from
plant (WWT).
the algae Thewhile
lipids, surrogate model
recycling is based
algae on afor
residue detailed
either model provided
anaerobic by Wassermann
digestion or combus-
et al. While
tion. with yield factors plant
the biogas of theismethanol
limited toreaction,
3.5 t/h as
(ca.given
3000inNm Table
3/h),1.depicting
[18]. a large size
bio-methane plant, the capacity of the biorefinery is unlimited.
Table 1. Yield factors of methanol reactor, derived from Wassermann et al. [18].
2.2.1. Algae Raw Material
– MeOH CO2 O2 H2 O CO H2
The biorefinery pathway uses microalgae biomass to produce liquid fuels from the
Yield factor (wt.-%) 61.9 2.3 0.2 35 0.2 0.4
algae-oil as well as biogas, recycle water and solid fertilizer from the remaining carbohy-
drates, protein and water shares. Industrial algae cultivation is a process that is still under
development and subject to a broad scientific discussion. Different cultivation reactor con-
cepts from open ponds, over photo-bioreactors and thin-layered cascade reactors exist.
Additionally, different strains of algae differ greatly in terms of productivity, lipid content
or even applied culture broth. The literature reports productivity values from 5 to a max-
Processes 2022, 10, 1298 7 of 30

The pure methanol is upgraded using the general concept of methanol-to-jet based on
consecutive methanol-to-olefins, olefins oligomerization and hydrofinishing. The product
distribution (given in Table 2) as well as hydrogen demand in hydrotreating are based on
the MtSynfuels process described by Liebner et al. [14]. The hydrofinishing step requires ca.
0.004 t H2 /tMeOH . Here, again wastewater is separated and treated in WWT for recycling
or disposal.

Table 2. Yield factors for Fischer–Tropsch reaction + upgrading as well as methanol-to-jet process
(data from [14,15]).

Component Jet Fuel Diesel Gasoline LPG Fuel Gas CO2 H2 O Crude Waxes
Yield Factor MTJ 0.2 0.163 0.046 0.039 - - 0.552 - -
Yield Factor FT-R - - - - 0.668 0.111 0.16 0.062
Yield Factor FT-U 0.71 0.03 0.24 - 0.02 - - - -

The FT route is modeled after the work of König and depicts a conversion with jet
fuel as the main product [15]. The detailed model was again consolidated to a limited
number of unit-operations. First, the raw materials are mixed (FT-M), afterwards CO2 and
H2 are converted to synthesis gas by reverse water-gas-shift reaction at temperatures of
900 ◦ C (RWGS). The required heat is provided internally by fuel gas combustion and small
amounts of additional steam. The synthesis gas is afterwards converted to Fischer–Tropsch
crude, waxes, wastewater and fuel gas in a FT-reactor at 225 ◦ C and approximately 25 bar
(FT-R). The fuel gas produced is used as a heating agent of the RWGS in a burner (FT-B).
The wastewater generated in the FT synthesis is sent to the wastewater treatment plant.
Crude and waxes are afterwards upgraded. Crude is sent directly to product splitting via
distillation. Waxes are first hydrocracked with a H2 demand of 0.006 tH2 /tWaxes . Afterwards,
the produced intermediate is also sent to the distillation column. Here, liquid fuels are
again separated and a small share of additional fuel gas is generated, which is sent to the
FT-B. The yield factors of the main Fischer–Tropsch reaction as well as FT-upgrading and
MTJ process are given in Table 2.
The capital costs for the MTJ are between 300–700 EUR/tJet (if scaled down to small
scale) [14]. Capital costs for small scale FT synthesis are reported to be between 270 and 800
EUR/tJet [13–15]. Additionally, Liebner states that MTJ can deliver a 15% cost reduction in
comparison to FT synthesis in small scale. Considering König’s rather conservative data for
FT synthesis of approximately 780 EUR/tJet , costs for MTJ are assumed to be roughly 85%
of this value, leading to base case capital costs of 660 EUR/tJet . Considering the 20-year
plant lifetime and 5% interest to calculate the capital recovery factor and assuming 10% of
yearly operational costs based on the fixed capital investment, total processing costs of ca.
1500 EUR/tJet are taken as base value (Equation (2)).
 
EUR 660 EUR/t
C MT J = 660 + ·10% = 1485 ≈ 1500 EUR/tJet (2)
t CRF

2.2. Biomass-to-X Process

The BtX process pathway is two-fold in this superstructure. The first path utilizes
biogas from a biogas plant with a composition of 65 vol. -% CH4 and 35 vol. -% CO2 for the
production of SynFeed in thermochemical synthesis. The second pathway depicts an algae-
based biorefinery to produce hydroprocessed esters and fatty acids (HEFA) from the algae
lipids, while recycling algae residue for either anaerobic digestion or combustion. While
the biogas plant is limited to 3.5 t/h (ca. 3000 Nm3 /h), depicting a large size bio-methane
plant, the capacity of the biorefinery is unlimited.

2.2.1. Algae Raw Material

The biorefinery pathway uses microalgae biomass to produce liquid fuels from the
algae-oil as well as biogas, recycle water and solid fertilizer from the remaining carbo-
Processes 2022, 10, 1298 8 of 30

hydrates, protein and water shares. Industrial algae cultivation is a process that is still
under development and subject to a broad scientific discussion. Different cultivation reac-
tor concepts from open ponds, over photo-bioreactors and thin-layered cascade reactors
exist. Additionally, different strains of algae differ greatly in terms of productivity, lipid
content or even applied culture broth. The literature reports productivity values from 5 to a
maximum of 60 g/m2 /d, while lipid content can rise up to 50 or even 70 wt.-% [22,23]. On
top of that, microalgae can be clustered into freshwater and saline strains, where the former
can also be used to treat municipal wastewater, while the latter is not dependent on fresh
water reserves [24,25]. During cultivation algae are strongly diluted with about 0.15 g/L to
4 g/L in open ponds and photo-bioreactors [26]. To effectively use the biomass, it has to
be harvested and dewatered. A typical primal harvesting technology is the sedimentation
basin which can increase the biomass concentration up to 1%. Afterwards, technologies
such as dissolved air flotation can be used to further increase biomass concentration to
10% [27]. Further dewatering can be achieved using mechanical filter presses or centrifuga-
tion which increase dry biomass concentrations to 20–30% [28]. For complete dewatering,
different drying technologies can be used [28]. However, they are energy-intensive. Thus,
algae-sludge is often further processed with a concentration of 20–30%.
Due to this broad spectrum of raw material and processing alternatives, thw literature
reports algae production costs between 145 and 1315 EUR/tDry-mass [22].
Because of the variety of technology options as well as scarcely available detailed
techno-economic models in the literature, the wet algae biomass is simply modeled as
a raw material which is produced on-site in this superstructure. It is assumed that the
algae-sludge is harvested and dewatered using conventional processes leading to a dry
matter concentration of 10 wt.-%. Algae costs of 265 EUR/tDry-mass based on results from
Davis et al. serve as base case costs [22]. These costs can be affiliated with a large-scale
production with cultivation productivity of 25 g/m2 /d [22]. Assuming 10 wt.-% dry
biomass this leads to 26.5 EUR/tAlgae-sludge which is rounded to 25 EUR/tAlgae-sludge . Davis
et al. use the Scenedesmus acutus strain of algae which has a molar chemical composition
of CH1.82 O0.49 N0.03 S0.001 P0.002 [22]. Next to about 30% lipids the biomass consists of 2.4%
ash, ca. 53% carbohydrates 13% proteins and 1.6% further cell mass [22]. However, they
also mention the well-known Chlorella vulgaris strain, which has a more or less similar
composition with slightly lower lipids concentration and higher carbohydrates content.
It is often discussed as major strain in biodiesel production [29]. In order to keep the
generic character of the algae production process the lipid content as well as the costs of
algae-sludge are varied in the later optimization study, thus showing more general effects
and not specifically for one chosen algae strain. Table 3 gives an overview of the key
parameters of the algae raw material.

Table 3. Key assumptions of algae biomass raw material (data adapted from [22,25]).

Fresh Dry
Base Costs CO2 Factor Lipid Content
Water Demand Biomass Content
25 45.9
−1.8 kg/kg 25 wt.-% 10 wt.-%
EUR/tAlgae-sludge t/tAlgae-sludge

2.2.2. Biomass Pretreatment and Lipid Extraction

Typical micro algae for fuels production exhibit lipid contents of 25 wt.-%. However,
only a certain share of those oils is directly available. Some is mixed with other components
and stored in cell walls, which reduces the amount of extractable oil. To break intercellular
walls and increase the available oil content, a pretreatment step can be included. Addition-
ally, this step increases the availability of the ligno-cellulosic residue for anaerobic digestion.
Various technologies from physical to thermal and chemical concepts are available. Some
examples are high-pressure homogenization, microwaving or milling and grinding. For a
broad overview we refer to Kamperidou et al. [30].
Processes 2022, 10, 1298 9 of 30

Processes 2022, 10, x FORInPEER

thisREVIEW
superstructure
a sonication process (SONIC) is implemented (see Figure 5). It 1
is assumed that 50% of the lipids are available without pretreatment. Using sonication, the
available share can be increased to 96% [7].
Make-up hexane
HEX-EXT

SONIC Algae Efficiency:

35 %
Accessable lipids: 96 %

Raw
algae sludge Supercritical
10 wt.-% CO2
dry mass

EMPTY Algae
Accessable lipids: 50 % Algae oil to
Efficiency: BIO-U
100 %

SUP-CO2-EXT

Algae residue
to AAD

Figure 5. Algae
Figure 5. Algae pretreatment pretreatment
and lipid and
extraction lipid section
process extraction process section
of renewable of superstructure.
refinery renewable refinery supe
ture.
To separately use the lipids and algae residue, an extraction step is necessary. Oil
2.2.3. Bio-Oil
extraction is commonly Upgrading
performed by chemical extraction using non-polar solvents. Two
process alternatives are Theimplemented:
extracted bio-oilThe is
commonly
upgradedknown
based hexane
on the extraction
UOP refining(HEX-EXT)
process (BIO-U
and the more advanced supercritical
process includes CO2 extraction
hydrotreating, (SUP-CO2 -EXT)
hydrocracking (see Figure 5).
and isomerization asWhile
well as produ
the hexane extraction only
tillation. Theextracts
data of35% of the available oils,
the techno-economic modelsupercritical COfrom
are extracted 2 extraction
Klein-Marcusc
has an efficiencyetofal.100% [7].process
[2]. His However, the considers
design energy consumption
a three-stageofhydrodeoxygenation
this alternative is also reactor at
substantially higher.
to produce saturated alkanes and propane. Afterwards, the alkanes are further trea
hydrocracking and hydro-isomerization. Unreacted hydrogen is recovered and cl
2.2.3. Bio-Oil Upgrading
using amine scrubbing, before internal recycling. The product distribution of the p
The extracted bio-oil isinupgraded
is depicted Table 4. Thebased on hydrogen
total the UOP refining
demandprocess
is 0.158(BIO-U). This. During
t H2 ⁄t Bio−oil
process includesscrubbing,
hydrotreating, hydrocracking and isomerization as well
high purity CO2 is produced. Because capital cost data wasas product dis-only bas
tillation. The data of the techno-economic model are extracted from Klein-Marcuschamer
rough estimates, the complete process design is modeled as one surrogate unit-ope
et al. [2]. His process ◦C
in thedesign considersmodel.
superstructure a three-stage hydrodeoxygenation
This unit-operation includes reactor at 350 data
the complete such as
to produce saturated
factors,alkanes
energyand propane.
demand and Afterwards,
capital costs.the alkanes are further treated by
hydrocracking and hydro-isomerization. Unreacted hydrogen is recovered and cleaned
using amine scrubbing, before
Table 4. Yield internal
factors recycling.
for the upgrading The product
of bio-oil distribution
(data adapted fromof [2]).
the process
is depicted in Table 4. The total hydrogen demand is 0.158 tH2 /tBio−oil . During amine
scrubbing, high purity Component
CO2 is produced. Because Jet fuel Gasoline
capital cost data Diesel
was onlyFuel
basedGas H2O CO2
on rough
Yield Factor (wt.-%) 41 22 6
estimates, the complete process design is modeled as one surrogate unit-operation in the 8 4 6
superstructure model. This unit-operation includes the complete data such as yield factors,
energy demand2.2.4. Biogas costs.
and capital Utilization and SynFeed Upgrading
After lipid extraction, remaining algae biomass and water can be further exp
Table 4. Yield factors
(seefor the upgrading
Figure of bio-oil
6). The wet (data
residue is adapted frominto
converted [2]).biogas by anaerobic digestion (A
Afterwards the gaseous stream and the liquid stream are separated. The liquid s
Component Jet fuel Gasoline Diesel Fuel Gas
contains water with diluted salts andHremaining
2O CO2
solid LPG
compounds. The solid comp
Yield Factor (wt.-%) 41 22 are separated6 from the liquid
8 4
using centrifugation 6
(CENTR) and13
can be sold as fer
[7]. The water can be purified and used as a raw material for electrolysis or directly
as a cultivation medium in algae cultivation. The second option suggests a co-locat
algae biomass production and renewable refinery, as it is assumed in this work. Th
eous product of anaerobic digestion is raw biogas with a composition of 65 vol. -%
and 35 vol. -% CO2 [7]. This biogas can be further utilized. Therefore, a biogas distr
 Processes 2022, 10, 1298 10 of 30

2.2.4. Biogas Utilization and SynFeed Upgrading

After lipid extraction, remaining algae biomass and water can be further exploited
(see Figure 6). The wet residue is converted into biogas by anaerobic digestion (AAD).
Afterwards the gaseous stream and the liquid stream are separated. The liquid stream
contains water with diluted salts and remaining solid compounds. The solid compounds
are separated from the liquid using centrifugation (CENTR) and can be sold as fertilizer [7].
Processes 2022, 10, x FOR PEER REVIEW water can be purified and used as a raw material for electrolysis or directly used as
The 11 aof 34
cultivation medium in algae cultivation. The second option suggests a co-location of algae
biomass production and renewable refinery, as it is assumed in this work. The gaseous
product of anaerobic digestion is raw biogas with a composition of 65 vol. -% CH4 and
(BG-DIST) is used
35 vol. -% CO to distribute among the biogas utilization or the purge gas treatment
2 [7]. This biogas can be further utilized. Therefore, a biogas distributor (BG-
section.
DIST) is used to distribute among the biogas utilization or the purge gas treatment section.

Purchased biogas from biogas plant

Wet algae residue from

- HEX EXT
- SUP-CO2-EXT
Biogas
- BG-PSA
Recycle water to Recycle water-Pool - TRIR

CENTR

Liquid phase
CENTR- Biogas
BG-DIST
DIST 65 vol.-% CH4
35 vol.-% CO2
AAD

Recycle water to WWT

Solid fertilizer to Fertilizer-Pool Biogas to
- HEAT GEN
- EL GEN

Figure 6. Algae residue treatment process section of renewable refinery superstructure.

Figure 6. Algae residue treatment process section of renewable refinery superstructure.

2.2.5.
2.2.5. Biogas
Biogas Utilization
Utilization and andSynFeed
SynFeedUpgrading
Upgrading
Biogas from
Biogas from anaerobic
anaerobicdigestion
digestionofofalgae
algaeresidue
residue as as
well
wellas as
biogas
biogasrawrawmaterial
material fromfrom
the biogas plant can be processed in similar ways (see Figure 7).
the biogas plant can be processed in similar ways (see Figure 7). The simplest way to com- The simplest way to
combust
bust biogas biogas to produce
to produce energy
energy (further
(further described
described in in purgegas
purge gastreatment
treatmentsection).
section).
Additionally, three different reforming technologies are included
Additionally, three different reforming technologies are included in the superstruc-in the superstructure:
Steam
ture: Steammethane (SMR)(SMR)
methane and autothermal (ATR) reforming
and autothermal of bio-methane
(ATR) reforming as well asas
of bio-methane direct
well as
biogas tri-reforming produce a CO2 /H2 mixture which can be used as feed material
direct biogas tri-reforming produce a CO2/H2 mixture which can be used as feed material
for the thermochemical synthesis (therefore called SynFeed). To utilize SMR and ATR
for the thermochemical synthesis (therefore called SynFeed). To utilize SMR and ATR up-
upstream biogas purification by pressure swing adsorption (BG-PSA) and vacuum pump
stream biogas purification by pressure swing adsorption (BG-PSA) and vacuum pump
(VP) separate CO2 [7]. The pure CO2 stream can be mixed with low-pressure CO2 from
(VP)
carbon captureCO
separate [7]. Theraw
to2provide purematerial
CO2 stream can be mixed synthesis,
for thermochemical with low-pressure CO2be
or it just can from
carbon
vented capture to provide SMR,
to the environment. raw material
ATR andfor thermochemical
TRIR are similar in that synthesis, or it just
they include can be
a series
vented
of reforming steps, namely pre-reforming at 500 C, main reforming to syngas as well series
to the environment. SMR, ATR and TRIR◦ are similar in that they include a as
of reforming
two-stage steps, namely
water-gas-shift reaction at 350 ◦ C and
pre-reforming at 500 ◦ C main
210°C, reforming
to convert CO and toH syngas
2 O to H as2 and
well as
two-stage
CO2 [31]. water-gas-shift
In the end, the raw reaction at 350
SynFeed is °C and 210
available at °C to convert CO
approximately 23 and
bar H
and2Ocooled
to H2 and
CO
down2 [31].
to 40In◦ C
theforend, the raw to
compression SynFeed is available
70 bar [31]. Differencesat in
approximately 23 bar
the process design and
arise cooled
in the
main synthesis
down to 40 °C forreaction. The SMRtounit
compression uses[31].
70 bar an externally
Differences fired
in isothermal
the processreactor 890 ◦in
designatarise C, the
where heat supply is provided by combustion of a share of the inlet
main synthesis reaction. The SMR unit uses an externally fired isothermal reactor at 890 bio-methane [31]. Hot
fluewhere
°C, gas is used
heat in heat recovery
supply and steam
is provided generation of
by combustion to aproduce
share of excess electricity.
the inlet ATR and[31].
bio-methane
TRIRflue
Hot bothgasutilize partial
is used oxidation
in heat usingand
recovery puresteam
oxygen instead of to
generation airproduce
at temperatures
excess around
electricity.
1000 ◦ C [31]. Due to internal heat supply, no excess heat is produced. The raw SynFeed has
ATR and TRIR both utilize partial oxidation using pure oxygen instead of air at tempera-
tures around 1000 °C [31]. Due to internal heat supply, no excess heat is produced. The
raw SynFeed has to be upgraded to meet the H2/CO2 ratio of the different thermochemical
synthesis process options. Therefore, excess hydrogen from SMR is separated by pressure
swing adsorption (H2-PSA) and excess CO2 from ATR and TRIR is separated using phys-
 Processes 2022, 10, 1298 11 of 30

to be upgraded to meet the H2 /CO2 ratio of the different thermochemical synthesis process
options. Therefore, excess hydrogen from SMR is separated by pressure swing adsorption
Processes 2022, 10, x FOR PEER REVIEW 12 of 34
(H2 -PSA) and excess CO2 from ATR and TRIR is separated using physical absorption with
Selexol as sorbent [31]. H2 - and CO2 recovery factors of the given technologies are 89% and
90%, respectively. Independent from the decision on reforming technology and upgrading,
In addition to reforming, bio-methane can be liquified at –152 °C by a reversed Ran-
the different SynFeed streams are distributed by a set of distributors to Fischer–Tropsch
kine process
synthesis (BM-LIQ). The
or compression resultingsynthesis.
for methanol liquefiedFischer–Tropsch
bio-methane depicts a liquid
synthesis fuel.
operates How-
at the
ever, it isoutlet
pressure only ofconsidered as atechnologies.
the reforming by-product in To this work
use the due to
SynFeed in the majorsynthesis
methanol differencea in
handling
compressor (SYNFEED COMP) is included. The techno-economic models of the reformingpro-
and transportation compared to the other fuels. Additionally, the liquifying
cess does not produce
technologies, upgradingaviation fuel
sections and(shares), which is
compressions arethe main
taken goala of
from the process
previous studylayout.
on
Data
biogasforreforming
the liquification
[31]. from of bio-methane is taken from Capra et al. [32].

LBM
to LBM-Pool
BM-LIQ

H2 to MP-H2 -DIST
H2-PSA

Flue gas SynFeed

Electricity H2/CO2 = 3

CH4 to SynFeed
VP
- HEAT GEN H2/CO2 = 4
- EL GEN SMR-DIST
CO2 to Air
CO2 - DIST CO2 to CO2-DIST

SynFeed
SMR
to FT-M
Biogas from SynFeed
BG-DIST Bio-Methane ATR-SELEXOL H2/CO2 = 3
BM-DIST
SynFeed
to MeOH SYN
Raw SynFeed
H2/CO2 = 2.8 SYNFEED COMP
CO2-PSA
ATR-DIST

O2 from
O2-DIST
ATR
O2 from
O2-DIST
CO2 to CO2-DIST
TRIR-SELEXOL
SynFeed
H2/CO2 = 3

Raw SynFeed
H2/CO2 = 1.8
Biogas from
TRIR-DIST
BG-DIST

TRIR

Figure 7. Biogas utilization and SynFeed upgrading process section of renewable refinery super-
Figure 7. Biogas utilization and SynFeed upgrading process section of renewable refinery superstructure.
structure.
In addition to reforming, bio-methane can be liquified at –152 ◦ C by a reversed Rankine
2.2.6. Purge
process Gas and
(BM-LIQ). TheWastewater Treatment
resulting liquefied bio-methane depicts a liquid fuel. However, it is
onlyDepending
considered on as athe
by-product in this work due to thecombustible
final process layout, different major difference
gasesinarise,
handling
whichandhave
totransportation
be burned in compared
order to keep to the other fuels.
emissions Additionally,
of unreacted the liquifying
hydrocarbons to process
a minimumdoesas
notwell
asproduce aviation
to increase fuel (shares),
the overall energywhich is theofmain
efficiency goal of the
the process. process
These layout.
gases are theData forstream
purge the
liquification from of bio-methane is taken from Capra et al. [32].
from methanol synthesis, raw biogas from either algae remnant treatment or raw material
(biogas plant)Gas
2.2.6. Purge as and
wellWastewater
as H2-by-products.
Treatment Gases can either be burned to produce steam for
internal heat supply (HEAT GEN) or electricity by application of a combined cycle power
Depending on the final process layout, different combustible gases arise, which have
plant (EL GEN) (see Figure 8) [7].
to be burned in order to keep emissions of unreacted hydrocarbons to a minimum as well
Arising wastewater from distillation columns, compression intercooling or from wet
as to increase the overall energy efficiency of the process. These gases are the purge stream
algae biomass can
from methanol be recycled
synthesis, and from
raw biogas usedeither
againalgae
in processes such as electrolyzers
remnant treatment or raw materialor as
steam input for biogas reforming processes. Another option is to release
(biogas plant) as well as H2 -by-products. Gases can either be burned to produce steam for remaining water
into the environment
internal heat supply (HEATas effluent.
GEN) or Anyway, inby
electricity both cases wastewater
application of a combinedhas cycle
to bepower
purified
first
plantin(EL
order
GEN) to (see
reduce
Figureimpurities
8) [7]. and potential remaining hydrocarbons. Wastewater
treatment is not modeled in detail but is considered to cost 2.5 EUR/t [3].
ocesses 2022, 10, x2022,
Processes FOR10,PEER
1298 REVIEW 12 of 30 13 o

H2 from
MP- H2-DIST Superheated steam
H2 from
LP-H2-DIST

Biogas from Flue gas

BG-DIST Purified water to
HEAT GEN - (HP)-AEL
- HP-PEMEL
Purge from
- SOEL
MeOH FLASH
Waste water from WWT
- MeOH DC Purified water to
- FT-R - ATR
- TRIR
Waste water from
- SMR
MTJ H2O-DIST
Waste water
CENTR-DIST

H2 from Purified water to

Waste water
Recycle Water-Pool
MP- H2-DIST Electricity from CO2 -COMP
H2 from Purified water to RWGS
LP-H2-DIST
Impurities to
Biogas from Flue gas Disposal-Pool
BG-DIST
EL GEN
Purge from
MeOH FLASH

Figure 8. Wastewater
Figure 8. Wastewaterand
and purge gastreatment
purge gas treatment process
process sectionsection of renewable
of renewable refinery superstruc
refinery superstructure.
ture.
Arising wastewater from distillation columns, compression intercooling or from wet
2.2.7. Rawbiomass
algae can beDistributors,
Materials, recycled and used again in processes such as electrolyzers or as steam
Products
input for biogas reforming processes. Another option is to release remaining water into the
Raw materials
environment include
as effluent. biogas
Anyway, fromcases
in both thewastewater
biogas plant with
has to an input
be purified firstlimit of 3.5 t/h
in order
well to
asreduce
different flue gases,
impurities pure O
and potential 2, wet algae-sludge,
remaining hydrocarbons. process
Wastewater water, air, monoethano
treatment is not
minemodeled in detailExcept
and hexane. but is considered to cost raw
for the biogas 2.5 EUR/t [3]. none of the raw materials is limi
material,
in terms
2.2.7. of
Rawavailability. External O
Materials, Distributors, 2 is assumed to be produced using cryogenic air se
Products
ration. Raw materials include biogas from the biogas plant with an input limit of 3.5 t/h, as
Theasmain
well products
different flue gases, ofpure
theOprocess system are
2 , wet algae-sludge, the water,
process fuel products. The main produ
air, monoethanolamine
are jet fuel, gasoline, diesel and LPG. The process alternatives derive thelimited
and hexane. Except for the biogas raw material, none of the raw materials is exact indistribut
terms of availability. External O2 is assumed to be produced using cryogenic air separation.
of fuels. However, in the end, they are summarized under one final product “fuels” w
The main products of the process system are the fuel products. The main products
theirare
respective lowerdiesel
jet fuel, gasoline, heatingand value.
LPG. The Due to this
process approach,
alternatives costs
derive as well
the exact as emissions,
distribution
be easily allocated
of fuels. However, tointhe
thedifferent
end, they main productsunder
are summarized depending
one finalon their energy
product content. N
“fuels” with
to the main
their fuel pool,
respective lower by-products
heating value. include
Due tomedium-pressure
this approach, costs hydrogen, oxygen, solid
as well as emissions,
can be easily allocated to the different main products
tilizer, liquified bio-methane and recycle water for algae cultivation.depending on their energy content.
Next to the main fuel pool, by-products include medium-pressure hydrogen, oxygen, solid
A set of 10 distributor units is implemented in the superstructure, which distrib
fertilizer, liquified bio-methane and recycle water for algae cultivation.
streams according to Table 5.
A set of 10 distributor units is implemented in the superstructure, which distribute
streams according to Table 5.
Table 5. Distributor names and process configuration of renewable refinery superstructure.

Distributor
Inlets Targets
Name
O2 from AEL/HP-
O2-DIST O2-Productpool, OXY, ATR, TRIR
PEM/SOEL/HP-AEL
HEAT /EL GEN, H2-Productpool, H2-MH
MP-H2-DIST H2 from H2-PSA
COMP, FT-M, HYDRO, BIO-U, MTJ
BM-DIST BM-PSA SMR/ATR, HEAT GEN, EL GEN
AEL/HP-PEM/SOEL/HP-AEL, ATR, TRI
Processes 2022, 10, 1298 13 of 30

Table 5. Distributor names and process configuration of renewable refinery superstructure.

Distributor Name Inlets Targets

O2 from AEL/HP-
O2 -DIST O2 -Productpool, OXY, ATR, TRIR
PEM/SOEL/HP-AEL
HEAT/EL GEN, H2 -Productpool,
MP-H2 -DIST H2 from H2 -PSA H2 -MH-COMP, FT-M, HYDRO,
BIO-U, MTJ
BM-DIST BM-PSA SMR/ATR, HEAT GEN, EL GEN
AEL/HP-PEM/SOEL/HP-AEL, ATR,
H2 O-DIST WWT
TRIR, SMR, Recycle water pool
SMR-DIST SMR H2 -PSA, SYNFEED COMP
ATR-DIST ATR ATR-SEL, SYNFEED COMP
TRIR-DIST TRIR TRIR-SEL, SYNFEED COMP
BG-DIST Biogas from AAD BG-PSA, TRIR, HEAT/ EL GEN
H2 -LM-COMP, H2 -LH-COMP,
LP-H2-DIST H2 from AEL, SOEL
HEAT/ EL GEN
Recycle water Productpool,
CENTR-DIST Wastewater from CENTR
Wastewater treatment

The flowsheet synthesis is investigated based on generic assumptions. However,

relevant data such as electricity or natural gas costs and emission factors are modeled after
the German energy system. Table 6 depicts main input parameters. Full load hours were
derived from a H2 supply optimization case study by Wassermann et al. [33]. Electricity
greenhouse gas (GHG) emissions and fresh water demand (FWD) were calculated based
on data from the ecoinvent database [33,34]. They reflect direct electricity purchase from
offshore wind farms at the German North Sea with the FLH derived from Wassermann
et al. Electricity costs for offshore wind energy are taken from a study published by
the Fraunhofer ISE [35]. Steam costs were derived using Aspen Plus simulation and
its integrated economic analyzer. The approach assumes natural gas combustion with
a cascade of four heat exchangers to produce superheated, high-, medium- as well as
low-pressure steam. Natural gas at costs were assumed to be 2.785 ct/kWh [12]. Costs of
unit-operations, natural gas and final cooling were allocated to the different steam types
based on their energy content. Table 7 presents costs, GHG emissions and FWD of major
raw materials and (by-)products.

Table 6. Assumptions on key parameters (data adapted from [3,12,18,33–38]).

Parameter Value Unit Parameter Value Unit

Interest rate 0.05 - Waste treatment costs 2.5 EUR/t
Costs of electricity 72 EUR/MWh Chilling costs 19.06 EUR/MWh
GHG emissions
0.0085 tCO2 −eq. /MWh Chilling GHG 0.4 tCO2 −eq. /MWh
of electricity
FWD of electricity 0.0997 tH2 O /MWh Chilling FWD 3.17 tH2 O /MWh
Steam GHG emissions 0.294 tCO2 −eq. /MWh Superheated Steam at 600 ◦ C 37.1 EUR/MWh
High pressure saturated
Steam FWD 0.485 tH2 O /MWh 37 EUR/MWh
steam at 330 ◦ C
Medium pressure saturated
Product load capPROD 200 ktMeOH /a 36.8 EUR/MWh
steam at 230 ◦ C
Low pressure saturated steam
Full load hours per year 4777 h/a 32.2 EUR/MWh
at 135 ◦ C
Process water 2 EUR/t Biogas availability 3.5 t/h
Processes 2022, 10, 1298 14 of 30

Table 7. Costs, greenhouse gas emissions and fresh water demand for raw materials and by-products
(data adapted from [3,34,36,39–42]).

Oxygen
Hydrogen Oxygen
– Purchase Biogas Jet Fuel Gasoline Diesel LPG
Product Product
(from ASU)
Costs (EUR/t) 21 350 2000 14.7 630 637 566 555
GHG emissions
0.585 −1.21 12.13 0.585 0.44 0.6 0.53 0.58
tCO2 −eq. /t )
FWD (tH2 O /t) 3.57 0.605 4.5 3.57 1.35 1.56 1.54 1.84
Lower heating
– 32.5 120 – 42.8 42.3 42.7 43.1
value

3. Methodology
3.1. Problem Statement
The following components and parameters of the superstructure model are given:
• Techno-economic sub-models for different unit-operations including:
# Split factors;
# Concentration requirements;
# Specific utility demands;
# Inlet- and outlet temperatures for heating/cooling demands;
# Capital costs functions;
# Lifetime;
# Cost factors for operation and maintenance, direct- and indirect capital costs;
# For reactor units: Stoichiometric and Yield parameters;
# For combined gas- and steam turbine / steam furnace: Efficiencies.
• Key parameters (costs, environmental burdens) for external utilities:
# Electricity;
# Steam (super-heated, high-, medium- and low-pressure);
# Cooling water;
# Refrigeration.
• Total plant full load operating hours (FLH).
• Interest rate for capital costs calculation.
• Key parameters for raw materials:
# Composition;
# Purchase costs;
# Environmental input balance;
# Minimum and maximum availability.
• Key parameters for byproducts:
# Revenues;
# Environmental avoided burdens.
• Key parameters for high temperature heat pump:
# Coefficient of performance (COP);
# Inlet- and outlet temperature;
# Linear capital costs.
• Given chemical components and their key parameters:
# CO2 equivalent;
# Lower heating value.
The OUTDOOR mathematical model is used, which implements the following constraints:
• Mass balances must be met;
• Splits are fixed based on given parameters for normal unit-operations;
Processes 2022, 10, 1298 15 of 30

• Splits are variable for distributor units; the outlet composition is fixed;
• The main product is a mixture of liquid hydrocarbons with respect to their lower
heating value;
• The yearly production of main product is set to 240,000 MWh which corresponds to
20,000 t/a fuel given a mean lower heating value of 12 MWh/t (43.2 MJ/kg);
• The model is not time-indexed but works with a fixed annual number of full load hours;
• A base case is investigated in detail with:
# Algae-sludge costs of 25 EUR/t;
# MTJ processing costs of 1500 EUR/t;
# Electricity price of 72 EUR/MWh;
# Algae lipid content of 25 wt.-%.
• Four different scenarios are investigated using the developed screening algorithm with:
# Scenario 1: Electricity price of 72 EUR/MWh and lipid content of 25 wt.-%;
# Scenario 2: Electricity price of 36 EUR/MWh and lipid content of 25 wt.-%;
# Scenario 3: Electricity price of 72 EUR/MWh and lipid content of 50 wt.-%;
# Scenario 4: Electricity price of 36 EUR/MWh and lipid content of 50 wt.-%.
• For every scenario a set of mutable parameters are calculated:
# MTJ processing costs: 680–2800 EUR/t;
# Algae-sludge purchase costs: 5–105 EUR/t.
With the given parameters and constraints, the optimization model minimizes the net
production costs of the fuel mixture as calculated in Equation (3). To do so, it also determines:
• The accurate mass- and energy-balances;
• The total GHG emissions and fresh water demand;
• Choice and size of technology;
• Variable splits for distributor units;
• Capital and operational costs for the sized unit-operations.

CAPEX + OPEX − PROFITS

minNPC = (3)
capPROD
For the collected data, all costs are implemented as EUR 2020. The complete Excel-
based data input sheet can be found in the Supplementary Information S1.

3.2. Solution Approach

To strengthen scientific discussion and the ability to recreate scientific output, the
optimization model is created with OUTDOOR (Open sUperstrucTure moDeling and
OptimizatiOn fRamework) [42]. OUTDOOR is an open-source python module which
combines object-oriented programming and data management with conventional alge-
braic modeling via the Pyomo modeling language. OUTDOOR models are written as
mixed-integer linear programming models (MILP) which allows the usage of different
open-source as well as state-of-the art commercial solvers. The base model is extensively
presented and discussed by Kenkel et al. [12]. It utilizes different concepts modelling and
programming concepts as well as approaches from techno-economic and life cycle analysis
calculations [43–46]. In the course of this work, the modeling framework was extended and
the model updated for necessary functions. Below, the general aspects of the framework
and the required added functionalities are described. The complete, updated optimization
model can also be found in the Supplementary Material S2. The updated version of the
python package can be found under https://github.com/PKenkel/OUTDOOR (accessed
on 29 May 2022).

3.2.1. OUTDOOR General Modeling Framework

OUTDOOR is a highly object-oriented software which aims for maximum automation
in the superstructure modeling and optimization procedure, but also provides a modular
 When the user included the case study data OUTDOOR’s automated algorithm does
the rest independently. The algorithm first creates an empty optimization model, which
is an object that inherits from Pyomos AbstractModel class and depicts empty equations
describing all substantial correlations of the model: Mass and energy balances, cost func-
tions, emissions and logic constraints. Additionally, the superstructure object is used to
Processes 2022, 10, 1298 16 of 30
generate a data file which depicts the model-readable data version of the case study. The
data file and the empty optimization model are used in a third step to create a filled model
instance, which then includes all required equations as well as all the required data for
toolset
the casefor general
study. Thismodeling and optimization
model instance is afterwardspurposes.
processed Thebydetailed
internalmodel architecture
optimizer classes
with
whichroles
in turnandtake
interaction
advantage of of
included
externalclasses
solversissuch
given as in the Appendix
Gurobi, Cplex or B, cbc.Figure
After A2.
the
Below,
model the superstructure
is solved, modeling
the included and optimization
data (sets, parameters, algorithm
calculatedwhich is implemented
variables and objective) in
OUTDOOR will be shortly explained using Figure 9. First, the user
are saved into OUTDOOR’s model output class in order to cut down on used memory has to input the data
of the case
storage. Thestudy.
modelInoutput
order class
to accelerate
saves alland
datasimplify
in common this python
process,dataOUTDOOR
structures provides
such as
object-oriented
lists and dictionaries. Additionally, OUTDOOR provides a set of analyzer classesstream
classes and data structures. Different unit-operation classes such as which
splitters,
are able to reactors
perform or techno-economic
product pools actand as blueprints for the
environmental unit-operation
analysis, objects thatsave
create flowsheets, are
necessary. These objects
results as txt-files aregraphs
or create created
andand parametrized
tables withanalysis,
for sensitivity data such as specific energy
respectively.
demand,
Nextcapital
to the cost functions
described or split factors.
capabilities, OUTDOOR Afterwards,
providesthe created
a set unit-operation
of utility functions
objects are added to an object of the superstructure class. This class depicts
which are used by the different classes. These include an automated piecewise-linearizer the boundary
conditions
for non-linear such as plant
capital costoperating
functions hours
as wellperas year, electricity
different automatedprices or yearly desired
optimization modes
product
such as multi-objective optimization and sensitivity analysis. The selectableIDE
load. Object instantiation can be carried out by using a python and the
predefined
included python API.
objective functions However, OUTDOOR
of OUTDOOR’s superstructure alsomodel
comesare with a MicrosoftofExcel-based
minimization net produc-
user interface that provides ready-made Excel sheet templates that
tion costs (NPC), net production greenhouse gas emissions (NPE) and net production can be used to fill in
unit-operation and boundary
fresh water demand (NPFWD). conditions data sets.

PYOMO Abstract-
Model with
"Empty" model
equations

Init. of Objects of External solver ProcessDesign

PYOMO Model- OUTDOOR -
User input OUTDOOR's unit- integration results output
OUTDOOR-internal instance with optimized
operation and
interaction "filled" model OUTDOOR's ProcessDesign
superstructure
equations integrated object
system classes
analysis tools
PYOMO-ready
formatted data file
of constructed
superstructure

Figure 9. Superstructure modeling and optimization algorithm implemented in OUTDOOR.

Figure 9. Superstructure modeling and optimization algorithm implemented in OUTDOOR.
3.2.2. Added Functionalities
When the user included the case study data OUTDOOR’s automated algorithm does
Prior
the rest to this work,The
independently. OUTDOOR
algorithmalready provided
first creates several
an empty functionalities
optimization for which
model, super-
structure
is an objectmodeling and optimization.
that inherits from Pyomos Nonetheless,
AbstractModel some features
class were empty
and depicts missingequations
to inves-
tigate process
describing synthesis correlations
all substantial for highly of
integrated
the model:novel
Massprocesses.
and energyOne was acost
balances, variable
func-
tions, emissions and logic constraints. Additionally, the superstructure object is used to
generate a data file which depicts the model-readable data version of the case study. The
data file and the empty optimization model are used in a third step to create a filled model
instance, which then includes all required equations as well as all the required data for
the case study. This model instance is afterwards processed by internal optimizer classes
which in turn take advantage of external solvers such as Gurobi, Cplex or cbc. After the
model is solved, the included data (sets, parameters, calculated variables and objective) are
saved into OUTDOOR’s model output class in order to cut down on used memory storage.
The model output class saves all data in common python data structures such as lists and
dictionaries. Additionally, OUTDOOR provides a set of analyzer classes which are able to
perform techno-economic and environmental analysis, create flowsheets, save results as
txt-files or create graphs and tables for sensitivity analysis, respectively.
Next to the described capabilities, OUTDOOR provides a set of utility functions which
are used by the different classes. These include an automated piecewise-linearizer for
non-linear capital cost functions as well as different automated optimization modes such as
multi-objective optimization and sensitivity analysis. The selectable predefined objective
functions of OUTDOOR’s superstructure model are minimization of net production costs
Processes 2022, 10, 1298 17 of 30

(NPC), net production greenhouse gas emissions (NPE) and net production fresh water
demand (NPFWD).

3.2.2. Added Functionalities

Prior to this work, OUTDOOR already provided several functionalities for superstruc-
ture modeling and optimization. Nonetheless, some features were missing to investigate
process synthesis for highly integrated novel processes. One was a variable
Processes 2022, 10, x FOR PEER REVIEW distribution
18 of 34
of mass flows instead of connections via fixed split factors. This would enable flowsheets
that use shares of intermediate products to satisfy demands in other unit-operations while
selling the remaining
distribution of mass flowsfractions
instead as by-products.
of connections viaThe
fixedsecond feature
split factors. that
This wasenable
would missing is an
approach
flowsheetsto handle
that uncertain
use shares input data
of intermediate and compare
products competing
to satisfy demands in technology alternatives
other unit-op-
with respect
erations while to this the
selling uncertainty. By applying
remaining fractions fitting methods,
as by-products. The secondthe economics
feature that wasof novel
missing is an approach
technologies still in thetodevelopment
handle uncertain input
phase candata
be and compare
compared tocompeting
each othertechnol-
even if overall
ogy alternatives with respect to this uncertainty. By applying fitting
processing costs of such options are still uncertain to some level, hence supporting methods, the eco- the
nomics of novel technologies still in the development phase can be compared
decision-making in early design phases. Within the scope of this work, both features are to each other
even if overall
developed andprocessing
integratedcosts of such options
in OUTDOOR are still uncertain
as presented to some level, hence
in the following:
supporting the decision-making in early design phases. Within the scope of this work,
both featuresUnits
Distributor are developed and integrated in OUTDOOR as presented in the following:

Normally,
Distributor Unitsunit-operations in OUTDOOR interact with each other by pre-defined spe-
cific split factors. These split factors describe separation performance as well as connection
Normally, unit-operations in OUTDOOR interact with each other by pre-defined spe-
between different
cific split factors. unit-operations.
These They separation
split factors describe are defined for the connection
performance as well as of one process u to
connection
another process u 0 for every chemical component i. In combination with the requirement
between different unit-operations. They are defined for the connection of one process u to
of mass process
another balanceu’(see model
for every in Supplementary
chemical component i. In Information),
combination withthesethe split factors build the
requirement
topology
of mass balanceof the(seesuperstructure. However,Information),
model in Supplementary one major disadvantage
these split factorsof pre-defined
build the split
parameters
topology of the is that they boundHowever,
superstructure. the topology one majorto (more or less) binary
disadvantage decisions.
of pre-defined splitAnpa-example
rameters
is given in is that
Figurethey10,bound
where OUT is the
the Ftopology to (more
outletorflow less) of
binary decisions.i of
component Anunit-operation
example u,
𝑂𝑈𝑇
u,i
is given in Figure 10, where 𝐹 is the outlet flow of component i of unit-operation
µu,u0 ,i is the pre-defined split𝑢,𝑖factor of component i from unit u to u and Fu,u0 ,i is the actual0 u,
𝜇𝑢,𝑢′ ,𝑖 of
flow is component
the pre-defined splitunit
i from factor u of
to component
u0 based oni from unit u to
the binary 𝐹𝑢,𝑢′ ,𝑖 is the
u’ and variable
decision of Yu0 that
depicts the choice of technology. It is clear, from the figure, that the given of
actual flow of component i from unit u to u’ based on the binary decision variable 𝑌𝑢′
topology can
that depicts the choice of technology. It is clear, from the figure, that the given topology
only result in either choosing to send 40% of i = 1 and 60% of i = 2 to units u = 2 and 60%
can only result in either choosing to send 40% of i = 1 and 60% of i = 2 to units u = 2 and
of i = 1 and 40% of i = 2 to u = 3 or to send the total stream to unit u = 4, otherwise mass
60% of i = 1 and 40% of i = 2 to u = 3 or to send the total stream to unit u = 4, otherwise
balances
mass balances are disobeyed.
are disobeyed. When Wheninvestigating
investigating highly
highlyintegrated
integrated processes,
processes, thisthiscan
can lead to
suboptimal
lead to suboptimal process layouts.
process Sometimes,
layouts. Sometimes, it could
it couldbe bebeneficial
beneficial totodistribute
distribute flows more
flows
variable.
more variable.This canThisbe canespecially
be especiallythe thecasecase
if intermediate
if intermediateproducts
productsare are used
used in other process
in other
stages
processas reacting
stages material.
as reacting In this
material. case,
In this it could
case, it couldbe bebeneficial
beneficial totoonly
onlyprocess
process thethe right
amount
right amount to satisfy the the
to satisfy demand,
demand, while
while thetherest
restis,is,e.g.,
e.g., sold to the
sold to themarket.
market.

Figure 10. Example topology based on classic split factors.

Figure 10. Example topology based on classic split factors.

In order to model such behavior, we developed the distributor unit, which works in
similar way to a multi-target valve. The detailed mathematical formulation can be found
in the model, provided in the Supplementary Information. The general concept is depicted
for a two-target distributor in Figure 11 and works as follows:
 𝐷𝐼𝑆𝑇
tributor unit is assigned an indexed parameter 𝑑𝑢,𝑘 which includes a binary number
system (e.g., [0, 0.1, 0.2, 0.4, 0.8, 0.01….]). Multiplication of the indexed parameter with
𝐷𝐼𝑆𝑇 𝑂𝑈𝑇
assigned binary variables 𝑌(𝑢,𝑢 ′ ,𝑘) and outlet flow 𝐹𝑢,𝑖 determines the slack variable
𝐷𝐼𝑆𝑇
𝐹𝑢,𝑢′ 𝑘,,𝑖 . The total split to a target is then derived by the sum of all shares combined with
Processes 2022, 10, 1298 the binary decision variable 𝑌𝑢′ (see Figure 11). In the final model, bi-linear equations 18are
of 30
linearized by Big-M formulations and additional constraints assure mass balance. Using
this approach, every distributor unit adds NB binary variables to the model, as shown in
Equation (4) Error!
In order Reference
to model source not
such behavior, we found.,
developedwhere NT is the number
the distributor of assigned
unit, which works in
targets and ND the degree of distribution accuracy.
similar way to a multi-target valve. The detailed mathematical formulation can be found in
the model, provided in the Supplementary Information. The general concept is depicted
𝑁𝐵 = 𝑁𝑇 ⋅ (1 + 4 ⋅ 𝑁𝐷) (4)
for a two-target distributor in Figure 11 and works as follows:

Figure 11. Concept representation of distributor unit.

Figure 11. Concept representation of distributor unit.
Prior to the optimization target processes, u0 are assigned to the distributor as well
Optimal Design Screening
as the accuracy of splitting Algorithm
in terms of number of calculated decimal points. During the
OUT of component i from the distributor u is calculated as
optimization,
So far, each the outlet
case flow
study inFOUTDOOR
u,i is optimized for one of the three predefined
the sumfunctions
objective of inlet flows
with coming from connected
a fixed parameter unit-operations.
set. Additionally, OUTDOOR This outlet
alreadyflow can be
includes
a functionality to automate sensitivity analysis where one parameter is modified stepsplit
distributed to the targets according to the defined accuracy. While the mass flow by
is variable,
step while allthe composition
other parametersofare each
set flow
constant.is equal. In order
However, to achieve
to compare thisorbehavior,
novel competing the
distributor unit is assigned an indexed parameter d DIST which includes a binary number
process alternatives with uncertain input data, it canu,k be practical to modify two parame-
system
ters, e.g.,(e.g., [0, 0.1, 0.2,costs
the processing 0.4, 0.8,
of two 0.01alternatives
. . . .]). Multiplication
at the sameof the indexed
time. parameter
This so-called two-waywith
DIST OUT DIST
assigned binary
sensitivity analysis resultsY(in
variables u,ua
and outlet flow Fu,i solution
0 ,k )multi-dimensional determines
matrix theincluding
slack variable Fu,u0 ,k,i .
outcomes
The total split to a target is then derived by the sum of all shares
such as minimized costs but also technology choice and flowsheet topology for every combined with the binary
pa-
decision variable
rameter pair. In order Y u0 to create and analyze such a multi-dimensional solution matrix, by
(see Figure 11). In the final model, bi-linear equations are linearized a
Big-M formulations
screening and additional
algorithm, inspecting economicconstraints
designsassure mass balance.
is developed Using this approach,
and implemented in OUT-
every distributor
DOOR. The proposed unitalgorithm
adds NB combinesbinary variables
two-way to sensitivity
the model,analysis
as shown in tailor-made
with Equation (4),
where NT graph
automated is the number of assigned
construction and works targets and ND the degree of distribution accuracy.
as follows:

NB = NT · (1 + 4 · ND ) (4)

Optimal Design Screening Algorithm

So far, each case study in OUTDOOR is optimized for one of the three predefined
objective functions with a fixed parameter set. Additionally, OUTDOOR already includes
a functionality to automate sensitivity analysis where one parameter is modified step by
step while all other parameters are set constant. However, to compare novel or competing
process alternatives with uncertain input data, it can be practical to modify two parameters,
e.g., the processing costs of two alternatives at the same time. This so-called two-way
sensitivity analysis results in a multi-dimensional solution matrix including outcomes such
as minimized costs but also technology choice and flowsheet topology for every parameter
pair. In order to create and analyze such a multi-dimensional solution matrix, a screening
algorithm, inspecting economic designs is developed and implemented in OUTDOOR. The
Processes 2022, 10, 1298 19 of 30

proposed algorithm combines two-way sensitivity analysis with tailor-made automated

graph construction and works as follows:
1. Definition of two parameters (which are, e.g., processing costs of two alternatives);
2. Definition of minimum and maximum value as well as step size for both parameters;
3. Definition of process alternatives which should be screened for;
4. Preparation of N x-values and N y-values based on step one and two;
5. Execution of two-way sensitivity analysis for N x N superstructure models by iteratively:
a. Modification of model instance parameters;
b. Execution of superstructure optimization for given model instance;
c. Extraction of single-optimization results and adding them to multi-dimensional
solution matrix;
6. Conversion of technology choice results to numerical scale;
7. Interpretation of multi-dimensional solution matrix for graph creation.
Steps 1–3 have to be performed by the user; step 4–7 are performed automatically by
OUTDOOR. To perform the two-way sensitivity analysis, OUTDOOR’s integrated opti-
mizer algorithm first calculates two lists of linearly spaced values for the chosen mutable
parameters based on the minimum and maximum value as well as step size. Afterwards,
an iteration of parameter modification, superstructure optimization and single-run re-
sults file saving is performed until every parameter combination is explored. Parameter
modification is implemented as an extension of the already existing sensitivity analysis
functionalities. Hence, OUTDOOR’s modular architecture is exploited to keep effort at a
minimum level. The total file, containing all results data of every independent optimization
is returned as an overall solution file. This multi-model-output object can be connected
to one of the aforementioned analyzer classes which includes a method to automatically
create a technology choice graph for a maximum of four different processes.
This graph method first extracts the mutable parameter lists and sets up a mesh grid
on an x- and y-axis, based on these parameters. Afterwards, the main results, namely
calculated net production costs (NPC) and technology choice for every calculated single-
optimization are extracted. The NPC are mapped over the mesh grid according to the given
parameter set. The technology choice is first translated into numeric values based on the
defined technology choices. This is achieved by utilizing a system of binary numbers where
single technology choices are references by an ascending binary number and a combination
of different choices is assigned the sum of the single numbers. An example is presented
in Table 8. In the end, the NPC are plotted as a contour graph on the x,y-meshgrid while
the numeric scale of technology choice is plotted as a heatmap with discrete numbers and
colors. Figure 12 presents the general mapping of NPC and technology choice from given
numbers in a mesh grid to the final graph. This graph provides a simple and intuitive way
to analyze technology choice and NPC based on two varying parameters.

Table 8. Binary mapping of technology choice.

Technology Numeric Mapping Value

Alternative 1 1
Alternative 2 2
Alternative 3 4
Alternative 4 8
Combination example: Alternative 1 and 3 1+4=5
Combination example: Alternative 1, 2 and 4 1 + 2 + 8 = 11
Processes 2022, 10, 1298 20 of 30
Processes 2022, 10, x FOR PEER REVIEW 21 of 34

Net production costs Technology choice

60 205 310 430 520 600 NPC:

600
3 3 3 1 1 1

100 210 305 420 540 550 to contours lines Technology choice 1+2 3 3 3 1 1 1
NPC: 500
Parameter Y

Parameter Y

Parameter Y
110 215 340 425 460 470 3 3 3 1 1 1
NPC: 400
to heatmap

130 220 330 340 350 380 Technology choice 2 3 3 3 1 1 1

NPC: 300

20 230 250 270 280 290 2 2 2 2 2 2

NPC: 200

50 15 120 125 135 140 Technology choice 1 2 2 2 2 2 2

Parameter X Parameter X Parameter X

Figure 12. Example building of output diagram of scanning algorithm.

Figure 12. Example building of output diagram of scanning algorithm.

4. Results and Discussion

4.1. Model
4.1. Model Characteristics
Characteristics and
and Computational
Computational Performance
Performance
The superstructure
The superstructure model
model consists
consists ofof 685,497
685,497 constraints
constraints andand 24,4823
24,4823 variables,
variables, ofof
which 1600 are binary. The base case optimization was performed on
which 1600 are binary. The base case optimization was performed on a server using four a server using
fourGHz
2.2 2.2 GHz
cores cores
with awith
totalaRAM
total of
RAM300 of
GB300 GB available.
available. UtilizingUtilizing
Gurobi Gurobi
9.1.2 as 9.1.2 as an
an optimi-
optimization
zation solver,solver, the base
the base case case
takestakes a total
a total 20332033 s resulting
s resulting in in
ananoptimal
optimalsolution
solutionwith
with aa
0.01% remaining
0.01% remaining optimality
optimality gap, which is
gap, which is Gurobi’s
Gurobi’s default
default threshold.
threshold. Of Of those
those 2033
2033 s,
s, 11%
11%
are required by OUTDOOR’s automated superstructure construction
are required by OUTDOOR’s automated superstructure construction and model building,and model building,
35% are
35% are invested
investedin intransferring
transferringthethepython
pythonmodel
modeltotothe Gurobi
the Gurobi solver
solverand 53%
and 53%areare
actually
actu-
required by the solver. It is notable that roughly 16% of the solver time is required
ally required by the solver. It is notable that roughly 16% of the solver time is required in order
in
to reduce
order the optimality
to reduce gap from
the optimality gap1% to 0.01%.
from 1% to 0.01%.
The screening
The screening algorithm
algorithm requires
requires numerous
numerous sequential
sequential optimizations.
optimizations. Therefore,
Therefore, thethe
different scenarios were calculated in parallel on an external server, where each scenario
different scenarios were calculated in parallel on an external server, where each scenario
was assigned a maximum number of four 2.2 GHz cores, with a total RAM of 300 GB.
was assigned a maximum number of four 2.2 GHz cores, with a total RAM of 300 GB.
During the screening, the single-run solver times vary, depending on the parameter set,
During the screening, the single-run solver times vary, depending on the parameter set,
and can consume considerably more time (up to >19,000 s) than the base case optimization.
and can consume considerably more time (up to >19,000 s) than the base case optimiza-
In order to reduce calculation time, a remaining optimality gap of 0.1% was allowed for the
tion. In order to reduce calculation time, a remaining optimality gap of 0.1% was allowed
screening algorithm, leading to total computing times of 42,044 to 87,514 s, depending on
for the screening algorithm, leading to total computing times of 42,044 to 87,514 s, depend-
the scenario.
ing on the scenario.
4.2. Base Case Results
4.2. Base Case Results
For the given base case: Electricity costs of 72 EUR/MWh, algae lipid content of
For the
25 wt.-%, given basecosts
algae-sludge case:ofElectricity
25 EUR/t and costsMTJ
of 72 EUR/MWh,
costs of 1500 EUR/t algae lipid content of 25
Jet are required for an
wt.-%, algae-sludge costs of 25 EUR/t and MTJ costs of 1500 EUR/t
optimal process design that depicts a highly integrated BtX and PtX process. The detailed Jet are required for an

optimal
flowsheet process design
is depicted that depicts
in Figure 13. In atotal
highly integrated
240,000 MWh/a BtX and PtX process.
(approximately 20 ktThe detailed
fuels/a) are
flowsheet at
produced is net
depicted in Figure
production costs13.ofIn
253total 240,000 MWh/a
EUR/MWh LHV
(approximately
(approximately 2993 20 kt
EUR/t fuels/a)
Fuels ).
are produced at net production costs of 253 EUR/MWh (approximately
The fuels shares are 47% jet fuel, 23% diesel, 18% gasoline and 12% LPG. Fuels are produced
LHV 2993 EUR/t Fuels).

The fuels shares are 47% jet fuel, 23% diesel, 18% gasoline and
to 52% based on MTJ using algae residue and additional biogas and 48% using hydrotreat- 12% LPG. Fuels are pro-
duced to 52% based on MTJ using algae residue and additional
ing of algae bio-oil. Additional CO2 is not used and H2 from electrolysis is only used in biogas and 48% using
hydrotreating
hydrotreating and of algae
not asbio-oil. Additional
main feed. CO2 is not
Algae-sludge usedasand
is used rawHmaterial
2 from electrolysis
and pretreatedis only
by
used in hydrotreating
sonication. Subsequentand lipidnot as mainisfeed.
extraction Algae-sludge
designed is usedCO
as supercritical as2 raw material
extraction. and
Lipids
pretreated
are afterwards by sonication.
refined to HEFASubsequentusing lipid extraction is designed
hydrodeoxygenation. Algaeas supercritical
residue CO 2 ex-
is converted to
traction.
biogas byLipids
anaerobicare afterwards
digestion. Liquidrefinedremnants
to HEFAis using hydrodeoxygenation.
treated by centrifugation which Algaeseparates
residue
is converted
solid fertilizertoasbiogas by anaerobic
a by-product digestion. Liquid
and remaining water forremnants
usage inisthe treated by centrifugation
co-located algae farm.
which
The separatesbiogas
remaining solid fertilizer
is mixed as a by-product
with additionally and remaining
bought biogaswaterfromfor usage plant
a biogas in theandco-
converted
located to raw
algae farm.SynFeed by TRIR. biogas
The remaining Part of the raw SynFeed
is mixed is upgraded
with additionally with selexol-based
bought biogas from
aCO 2 capture.
biogas plantThe and captured
converted CO2toisraw
not required
SynFeedanymore
by TRIR.and Part vented.
of theThe rawlow-detail
SynFeed modelis up-
of algaewith
graded cultivation does not
selexol-based COinclude theThe
2 capture. acquisition
capturedofCO CO is. not
2 2 However,
required in anymore
the proposed and
flowsheet, vented CO from the TRIR-SEL, BIO-U and HEAT GEN
vented. The low-detail2 model of algae cultivation does not include the acquisition of CO2. process could provide
approximately
However, in the30% of the cultivation
proposed flowsheet, CO 2 demand.
vented CO2 fromThethepurified
TRIR-SEL,SynFeed BIO-Uis mixed
and HEAT with
the remaining
GEN process could SynFeed
provide to meet the specification
approximately 30% of of
themethanol
cultivation synthesis.
CO2 demand. The produced
The puri-
SynFeed
fied SynFeedis compressed
is mixed with to 70thebar and converted
remaining SynFeedto methanol,
to meet theand methanol of
specification is upgraded
methanol
 required heat via partial oxidation. Purge gas from the methanol synthesis is combusted
to produce superheated steam, which is used to decrease the external steam demand.
Wastewater from methanol distillation, MTJ and BIO-U is treated in WWT first, and af-
terwards used as a raw material in TRIR and HP-AEL.
Heat integration reduces the external heat demand from ca. 6.49 MW to 0.02 MW. Ca
Processes 2022, 10, 1298 18% of the recovered heat is produced in purge gas treatment and the remaining 82% 21 of 30
is
gained from waste heat of methanol synthesis and flash as well as hydrodeoxygenation
of bio-oils and intercooling of the TRIR process. The model does not include detailed HEX-
matching.
to fuels byHowever, based on thealkaline
MTJ. A high-pressure given temperature levels,
electrolysis unit a first indication
produces of matches
small amounts of H2
can be provided. In such a matching, high-temperature heat from
which are utilized in hydrodesoxygenation of bio-oil (BIO-U) and hydrotreating in HEAT GEN, MeOH
MTJ.
SYN,OTRIR
The and BIO-U
2 by-product would
of the HP-AEL be used forin
is used medium
TRIR totemperature
produce the demand
required in BIO-U.
heat Heat
via partial
from cooling
oxidation. in MeOH
Purge FLASH
gas from and TRIRsynthesis
the methanol would beiscoupled
combustedwithtothe distillation
produce column
superheated
of the SUP-CO
steam, which is2-EXT.
used toFinally, waste
decrease theheat fromsteam
external BIO-Udemand.
or TRIR would be used
Wastewater fromin the AAD.
methanol
Additionally,
distillation, MTJ18.11
andMW of cooling
BIO-U utility
is treated are required.
in WWT first, and The total electricity
afterwards used as ademand is ca.
raw material
30 MW, and
in TRIR of which 20 MW are required by the HP-AEL.
HP-AEL.
4.89 MWel

61.42 t/h
supercritical CO2
0.16 t/h CO2 (vented)
1.39 MWcool
0.33 MWel 0.53 MWcool 4.63 t/h
CO2 7.1 MWcool
1.85 MWel 0.11 t/h waste water
4.3 MWheat to WWT
90.56 t/h
algae sludge 63.59 t/h 2.17 t/h algae-oil 24.15 MWh/h fuels mixture
FUELS
UOP-R
0.121MWchill
SONIC 1.5 MWheat
0.1 MWel
FUR

26.09 MWh/h fuels mixture

SUP CO2-EXT 0.03 MWcool
88.39 t/h wet residue

2.75 t/h air

5.63 t/h
SynFeed 1.14 MWsteam
MeOH FLASH
1.01 t/h
0.27 t/h purge gas
SynFeed
0.42 t/h
TRIR
Pure O2
TRIR-SEL SYNFEED 1.05 MWcool
3.39 t/h biogas COMP 0.11 MWel 0.4 MWcool
AAD from algae 0.08 MWel 4.9 t/h methanol
6.96 t/h
0.69 MWheat SynFeed
0.34 MWel 3.5 t/h biogas MeOH
MTJ
externally bought 0.77 MWel DC
3.79
85 t/h liquid residue 5.67 MWcool MeOH SYN MWcool
0.08 t/h
1.27 MWel 2.79 t/h waste water
process water 5.6 t/h water REC WATER
WWT FOR ALGAE FARM
2.72 t/h waste water
0.21 MWel 83.99 t/h recylce water
3.3 t/h water

CENTR
0.35 t/h H2

1 t/h solid fertilizer

0.02 t/h H2
FERTILIZER
Utility information: HP-AEL
2.94 t/h O2

Total net electricity demand: 29.95 MW

Total net heating demand: 0.02 MW
Total net cooling demand: 18.11 MW
Total energy integration: 6.47 MW 3.48 MWcool
Total heat pump supply: 0 MW 20 MWel

Figure
Figure 13.
13. Process
Process flow
flow diagram of NPC-optimized
diagram of renewable refinery
NPC-optimized renewable refinery base
base case.
case.

Error! Reference reduces

Heat integration source not
the found.
externalTable
heat 9demand
presentsfrom
the cost breakdown
ca. 6.49 of the
MW to 0.02 MW. NPC.
Ca
It canofbe
18% seen
the that theheat
recovered major cost drivers
is produced in are capital
purge costs withand
gas treatment 43.3%theand raw materials
remaining 82% is
gained
with from the
27.5%; waste heatand
third of methanol synthesis
fourth largest shareand
areflash as wellcosts
electricity as hydrodeoxygenation
(17%), and operating of
bio-oils
and and intercooling
maintenance (16.6%).of the TRIR process. The model does not include detailed HEX-
matching.
FigureHowever,
14 shows based on the given
the breakdown temperature
of capital levels,
costs (left) anda electricity
first indication
demandof matches
(right).
can be provided.
Largest capital costInshares
such aarematching,
generated high-temperature
by MTJ (24.3%), heatTRIRfrom HEAT
(15.6%), GEN, MeOH
anaerobic diges-
SYN, TRIR and BIO-U would
tion (16.6%) and BIO-U (17.8%). be used for medium temperature demand in BIO-U. Heat
fromElectricity
cooling inisMeOH FLASH and TRIR would be coupled with the distillation
mainly consumed by the high-pressure alkaline electrolysis and the H2 column
of the SUP-CO
compressor 2 -EXT.
(66.8%) asFinally,
well as waste heat from BIO-U
the supercritical or TRIR (16.3%).
CO2 extraction would beRaw used in the AAD.
material costs
Additionally,
mainly originate18.11 MW
from of algae-sludge
raw cooling utilitypurchase
are required.
(64.7%)The total
and rawelectricity demand is ca.
biogas (35%).
30 MW, of which 20 MW are required by the HP-AEL.
Table 9 presents the cost breakdown of the NPC. It can be seen that the major cost
drivers are capital costs with 43.3% and raw materials with 27.5%; the third and fourth
largest share are electricity costs (17%), and operating and maintenance (16.6%).
Figure 14 shows the breakdown of capital costs (left) and electricity demand (right).
Largest capital cost shares are generated by MTJ (24.3%), TRIR (15.6%), anaerobic digestion
(16.6%) and BIO-U (17.8%).
 Processes 2022, 10, x FOR PEER REVIEW 23

Processes 2022, 10, 1298 22 of 30

Table 9. Net production cost distribution of fuel mixtures in base case optimization.
Table 9. Net production cost distribution of fuel mixtures in base case optimization.
Position Share (%) EUR/MWh EUR/tF
Position Share (%)
Capital costs EUR/MWh43.3 EUR/t
110
Fuel 1299
Capital costs Raw materials 43.3 11027.5 70
1299 823
Raw materials Electricity 27.5 70 17 82343 509
Electricity 17
Operating and Maintenance 4316.6 50942 497
Operating and Maintenance 16.6 42 497
Heat integration/Refrigeration
Heat integration/Refrigeration 0.3 1
0.3 9
1 9
Profits Profits –4.7 12–4.7 12
141 141

Figure
Figure 14. Capital cost14.
andCapital costdemand
electricity and electricity
breakdowndemand breakdown
of renewable of renewable
refinery refinery base case op
base case optimization.
zation.
Electricity is mainly consumed by the high-pressure alkaline electrolysis and the H2
compressor (66.8%) When comparing
as well the combined
as the supercritical CO2PBtX refinery
extraction with a Raw
(16.3%). purely electricity-based
material costs MT
mainly originateFT refinery,
from rawa algae-sludge
cost reductionpurchaseca. 21% (64.7%)
and 28%and canrawbe achieved,
biogas (35%). respectively. If comp
to a stand-alone biorefinery, where algae residue
When comparing the combined PBtX refinery with a purely electricity-based is converted to a liquid
MTJbio-methane
or
product, a cost reduction of 11.5% is achieved. A
FT refinery, a cost reduction ca. 21% and 28% can be achieved, respectively. If compared comparison to the literature is no
to a stand-alonesimple due to thewhere
biorefinery, numerous algaeassumptions. Wassermann
residue is converted et al. reported
to a liquid bio-methane lower MTJ-b
by-product, ajet fuel
cost costs of ca.
reduction 2225 EUR/t
of 11.5% Jet [47]. However,
is achieved. A comparison they toalso
theused reduced
literature electricity
is not as cos
simple due to50the EUR/MWh
numerousand lower MTJ process
assumptions. Wassermann costs of about
et al. 400 EUR/t
reported lower based on large scale
Jet MTJ-based

jet fuel costs plications

of ca. 2225[47]. EUR/tIf both factors
Jet [47]. are included
However, they alsoin used
the comparison, the totalcosts
reduced electricity costs of fue
of 50 EUR/MWh againand in the
lower sameMTJ range. König
process costscalculated
of about 400FT-based
EUR/tjet Jet fuel
based prices
on of
large 3380
scale EUR/tFuel
However, he had increased electricity costs of 104 EUR/MWh,
applications [47]. If both factors are included in the comparison, the total costs of fuel are but a substantially la
plant range.
again in the same with 526 ktJet/acalculated
König output and high fulljet
FT-based load
fuelhours
prices ofof8760
3380h/a, leading
EUR/t Fuelto reduced ca
[15].
However, hecost hadshares
increased[15].electricity
In general, all of
costs ofthe
104results are in the
EUR/MWh, butsame region depending
a substantially larger on the
plant with 526 senktassumptions.
Jet /a output and high full load hours of 8760 h/a, leading to reduced
capital cost sharesIn[15]. terms In of environmental
general, all of theimpacts,
results aretheinoptimal
the same base case comes
region depending with on negative gr
house gas emissions of –3.7 t CO2 ⁄t Fuels , while requiring 960 t H2 O ⁄t Fuels of water. W
the chosen assumptions.
In termscompared
of environmental impacts, the
to the stand-alone optimal
options, base case comes
greenhouse with negative
gas emissions are in thegreen-
same regio
house gas emissions
all options. of –3.7
WatertCOdemand,
2
/tFuels , while
on the requiring 960 tis
other hand, O /tFuels matter.
H2another of water.Algae When cultivation
compared to quires
the stand-alone
substantiallyoptions, moregreenhouse
water than gas water
emissions are in theand
electrolysis same regioncapture.
carbon for Du
all options. Water
avoided demand,
burdens on the
for other hand, iselectricity-based
by-products, another matter. Algae processescultivation requiresnegative
even generate
substantially termore water than
demands of ca.water–7.5 electrolysis
t H2 O ⁄t Fuels .and carbon
Table capture.costs
10 presents Due and
to avoided bur-
GHG emissions of
dens for by-products, electricity-based processes even generate negative
ventional production of the given yearly product loads considering the actual water demands of pro
ca. –7.5 tH2 O /t Fuels . Table and
distribution 10 presents
reference costs
GHG andemissions
GHG emissions
and costsof conventional
from Table 7. production
Based on these va
of the given yearly product loads considering the actual product
and the calculated costs and emissions of the renewable refinery, CO distribution and reference
2 abatement cos
GHG emissions ca. and
561 costs
EUR⁄fromt CO2 Table 7. Based
arise (see Tableon11). these values and the calculated costs and
emissions of the renewable refinery, CO2 abatement costs of ca. 561 EUR/tCO2 arise (see
Table 11).
 Processes 2022, 10, x FOR PEER REVIEW 24 of 34
Processes 2022, 10, 1298 23 of 30

Table 10. Calculated yearly production, greenhouse gas emissions and costs of conventional fuels
Table 10. Calculated yearly production, greenhouse gas emissions and costs of conventional
production.
fuels production.
– Jet Fuel Diesel Gasoline LPG Total
–
Yearly production (t/a) Jet Fuel9564 Diesel
4566 Gasoline
3705 LPG
2457 Total
20,292
Yearly
GHG ofproduction
conventional(t/a)produc-9564 4566 3705 2457 20,292
GHG of conventional 4227 2402 2216 1432 10,277
tion (t/a) 4227 2402 2216 1432 10,277
production (t/a)
Costs of conventional produc-
Costs of conventional 6,025,0392,584,356
6,025,039 2,584,3562,360,085
2,360,085 1,363,635
1,363,635 12,333,396
12,333,396
tion (EUR/a)
production (EUR/a)

Table 11. Calculated CO2 abatement costs of renewable refinery base case.
Table 11. Calculated CO2 abatement costs of renewable refinery base case.
GHG Emission of
Costs ofofCon-
Costs Costs
Costs of
of Re- GHG of Renewa- CO2 Abatement
GHGConventional
Emission of GHG
ventional
ConventionalPro- newable
RenewableRefin- ble Refinery CO2 Abatement
Costs
Conventional
Production of Renewable
Production
duction (EUR/a) eryRefinery (𝐭 𝐂𝐎(t
(EUR/a) Production (tCO /a) Refinery ⁄ 𝐚 ) Costs (EUR/t
(𝐄𝐔𝐑 ⁄𝐭 𝐂𝐎CO )2 )
𝟐 CO2 /a)
(EUR/a) (EUR/a) (𝐭 𝐂𝐎𝟐 ⁄𝐚)2 𝟐

12,333,396
12,333,396 60,696,977
60,696,977 10,277
10,277 –75,979
–75,979 561
561

4.3. Optimal Design Screening Algorithm Results

4.3. Optimal Design Screening Algorithm Results
Figure 15
Figures 15 and
and 16 Figure 16 present
present the of
the results results of the optimal
the optimal design screening
design screening algorithm
algorithm for the
for the electricity price of 72 EUR/MWh. Figure 15 depicts an
electricity price of 72 EUR/MWh. Figure 15 depicts an algae lipid content of 25 wt.-% algae lipid content of 25andwt.-
% and Figure 16 depicts a lipid content
Figure 16 depicts a lipid content of 50 wt.-%. of 50 wt.-%.
ItItcan
canbebeseen
seen that,
that, forfor
72 72 EUR/MWhand
EUR/MWh el
el and 25% lipids, fuel costs vary between ca. 177
25% lipids, fuel costs vary between ca. 177 and
andEUR/MWh
331 331 EUR/MWh(2092–3912 LHV (2092–3912 EUR/t) for algae costs between 5 and 105 EUR/tAlgae-sludge
EUR/t) for algae costs between 5 and 105 EUR/tAlgae-sludge
LHV
and MTJ costs between 680 and 2800 EUR/t Jet. Four distinct operating windows appear for
and MTJ costs between 680 and 2800 EUR/tJet . Four distinct operating windows appear
different
for different algae
algae costs andand
costs total MTJ
total processing
MTJ processing costs. For For
costs. low low
algaealgae
and and
MTJ MTJ
costs,costs,
a com-
a
bination such as presented in the base case is most profitable.
combination such as presented in the base case is most profitable. For MTJ costs higher For MTJ costs higher then
15001500
then EUR/t Jet, this,step
EUR/t is replaced by Fischer–Tropsch synthesis. If algae costs exceed ap-
Jet this step is replaced by Fischer–Tropsch synthesis. If algae costs exceed
proximately 40
approximately 40EUR/t
EUR/tAlgae-sludge , a purely electricity-based production is chosen based on
Algae-sludge , a purely electricity-based production is chosen based on
methanolsynthesis
methanol synthesis forfor
MTJ MTJ costs
costs up toupca.
to2400
ca. 2400
EUR/t EUR/t Jet. For even higher costs, an FT-
Jet . For even higher costs, an FT-based
based production
production is most economic.
is most economic.

Figure15.
Figure 15. Net production costs
costs (contour
(contourlines)
lines)and
andtechnology
technologychoice
choice(heatmap) of of
(heatmap) optimized re-
optimized
newable refinery
renewable refinerydepending
dependingon
onalgae
algaecosts
costsand
andMTJ
MTJcosts
costsin
inscenario
scenario1.
1.

If the lipid content in the raw algae is elevated (Figure 16), the total fuel costs range
changes to 2150–3912 EUR/t. The maximum cost value is still associated with a purely
 These processes are the most expensive ones in the total process design, which makes
capacity reduction a good cost saver.
Additionally, to the four operating windows recorded previously, now a purely bio-
based production is most economic for low algae costs of up to 35 EUR/tAlgae-sludge and MTJ
costs higher than 1000–1250 EUR/tJet. Furthermore, the operating window for an inte-
Processes 2022, 10, 1298 24 of 30
grated design is increased for higher algae costs up to 70–95 EUR/tAlgae-sludge depending on
the MTJ costs.

Figure 16.
Figure 16. Net
Net production
productioncosts
costs(contour
(contourlines)
lines)and
andtechnology
technology choice
choice(heatmap) of optimized
(heatmap) re-
of optimized
newable refinery
renewable refinerydepending
dependingon
onalgae
algaecosts
costsand
andMTJ
MTJcosts
costsininscenario
scenario2.2.

If the lipid
Figure content
17 and in the
Figure 18 raw algae
display theis screening
elevated (Figure
results 16),
for the total fuel costs
an electricity pricerange
of 36
changes
EUR/MWh. to 2150–3912
Figure 17 againEUR/t. The maximum
depicts an algae lipid costcontent
value isofstill
25%,associated with18a depicts
while Figure purely
electricity-based
a lipid content ofproduction; hence from
50%. It is evident it is independent
Figure 17 thefrom totalthe lipid
costs content.
range The minimal
for decreased elec-
price is slightly elevated compared to a lower lipid content.
tricity price also decreases to ca. 165–263 EUR/MWh (1950–3109 EUR/tFuel). This Nonetheless, the costs for
is equiv-
combined
alent to a 10%process
to 20%concepts are on average
cost reduction comparedaboutto 10%
thecheaper compared price.
higher electricity to the Especially
case with
25% lipids.electricity-based
for purely This can be explained by thethe
production, bio-based
share ofnature of the
electricity combined
costs is high,process: While
explaining the
alkaline
increased electrolysis
cost reductionplaysata the
rolehigh-end
in the overall
of theprocess scheme,
price range. the mainitfeedstock
In general, for that
can be seen the
products
the operatingis based
windowson algae. If the content
for stand-alone MTJ ofand
lipidsFT which can beprocesses
production converted aredirectly
increasedto
fuels rises, this leads to smaller capacities in anaerobic digestion, biogas
compared to the cases with higher electricity price. Nonetheless, for low algae costs up to reforming and
MTJ.
30–40These
EUR/t processes are the most expensive ones in the total process design, which makes
Algae-sludge a combination with methanol or Fischer–Tropsch synthesis is still
capacity reduction a good
beneficial. As shown in Figure cost saver.
17, an operating window for a stand-alone biorefinery also
Additionally, to the
emerges for very low algae costs four operating
of 5 EUR/twindows recorded previously, now a purely bio-
Algae-sludge and MTJ costs above 1000 EUR/tJet.
based production is most economic for low algae costs of up to 35 EUR/tAlgae-sludge and MTJ
costs higher than 1000–1250 EUR/tJet . Furthermore, the operating window for an integrated
design is increased for higher algae costs up to 70–95 EUR/tAlgae-sludge depending on the
MTJ costs.
Figures 17 and 18 display the screening results for an electricity price of 36 EUR/MWh.
Figure 17 again depicts an algae lipid content of 25%, while Figure 18 depicts a lipid
content of 50%. It is evident from Figure 17 the total costs range for decreased electricity
price also decreases to ca. 165–263 EUR/MWh (1950–3109 EUR/tFuel ). This is equivalent
to a 10% to 20% cost reduction compared to the higher electricity price. Especially for
purely electricity-based production, the share of electricity costs is high, explaining the
increased cost reduction at the high-end of the price range. In general, it can be seen that
the operating windows for stand-alone MTJ and FT production processes are increased
compared to the cases with higher electricity price. Nonetheless, for low algae costs up to
30–40 EUR/tAlgae-sludge a combination with methanol or Fischer–Tropsch synthesis is still
beneficial. As shown in Figure 17, an operating window for a stand-alone biorefinery also
emerges for very low algae costs of 5 EUR/tAlgae-sludge and MTJ costs above 1000 EUR/tJet .
Processes 2022, 10, 1298 25 of 30
Processes 2022, 10, x FOR PEER REVIEW 26 of 34

Figure 17. Net production costs (contour lines) and technology choice (heatmap) of optimized re-
newable refinery depending on algae costs and MTJ costs in scenario 3.

Figure 18. Net production costs (contour lines) and technology choice (heatmap) of
optimized renewable refinery depending on algae costs and MTJ costs in scenario 4.
shows the results for a lipid content of 50% for a decreased electricity price. It fol-
lows the logic of the other graphs. Both stand-alone electricity-based and bio-based pro-
duction operating windows are increased. For low algae costs, pure algae-based produc-
tion is most economic. Due to high lipid content, this is the case for algae costs up to 40
EUR/t. The optimal region for integrated process design is very small. Due to the low
electricity price, stand-alone MTJ or FT is quickly more economic than a combined pro-
cess. The total cost range is between 156 and 262 EUR/MWh (1844–3109 EUR/t). The max-
imum cost value is again similar to scenario 3, due to the independency of the FT process
from the algae lipid content. The minimum value is slightly lower, due to more economic
usage
Figure of
Figure 17.algae-oil
17. Net and lower
Netproduction
production
costsCAPEX
costs
(contour for
(contour algae
lines)
lines) and residue
and treatment,
technology
technology choice
choice similar to of
(heatmap)
(heatmap) scenario 1 and
of optimized
optimized re-
2.
renewable refinery depending on algae costs and MTJ costs in scenario
newable refinery depending on algae costs and MTJ costs in scenario 3. 3.

Figure 18. Net production costs (contour lines) and technology choice (heatmap) of
optimized renewable refinery depending on algae costs and MTJ costs in scenario 4.
shows the results for a lipid content of 50% for a decreased electricity price. It fol-
lows the logic of the other graphs. Both stand-alone electricity-based and bio-based pro-
duction operating windows are increased. For low algae costs, pure algae-based produc-
tion is most economic. Due to high lipid content, this is the case for algae costs up to 40
EUR/t. The optimal region for integrated process design is very small. Due to the low
electricity price, stand-alone MTJ or FT is quickly more economic than a combined pro-
cess. The total cost range is between 156 and 262 EUR/MWh (1844–3109 EUR/t). The max-
imum cost value is again similar to scenario 3, due to the independency of the FT process
from the algae lipid content. The minimum value is slightly lower, due to more economic
usage of algae-oil and lower CAPEX for algae residue treatment, similar to scenario 1 and
2.

Netproduction
18. Net
Figure 18. productioncosts
costs(contour
(contour lines)
lines) andand technology
technology choice
choice (heatmap)
(heatmap) of optimized
of optimized re-
newable refinery
renewable depending
refinery dependingonon
algae costs
algae and
costs MTJ
and costs
MTJ inin
costs scenario 4. 4.
scenario

Figure 18 shows the results for a lipid content of 50% for a decreased electricity
price. It follows the logic of the other graphs. Both stand-alone electricity-based and bio-
based production operating windows are increased. For low algae costs, pure algae-based
production is most economic. Due to high lipid content, this is the case for algae costs up to
40 EUR/t. The optimal region for integrated process design is very small. Due to the low
electricity price, stand-alone MTJ or FT is quickly more economic than a combined process.
The total cost range is between 156 and 262 EUR/MWh (1844–3109 EUR/t). The maximum
cost value is again similar to scenario 3, due to the independency of the FT process from
the algae lipid content. The minimum value is slightly lower, due to more economic usage
of algae-oil and lower CAPEX for algae residue treatment, similar to scenario 1 and 2.
All four figures indicate that for stand-alone PtX processes MTJ is more economic up to
MTJ costs of 2000–2300 EUR/tJet . Although the Fischer–Tropsch synthesis produces fuels at
Figure 18. Net production costs (contour lines) and technology choice (heatmap) of optimized re-
1160 EUR/tJet at this capacity, it is less efficient. The reduced efficiency originates from the
newable refinery depending on algae costs and MTJ costs in scenario 4.
Processes 2022, 10, 1298 26 of 30

large usage of internally produced fuel gas for the reverse water-gas-shift reactor. Hence,
only 22% of the FT inlet is converted into usable fuels compared to ca. 28% in MTJ. Due
to this efficiency disadvantage and an increased H2 demand for synthesis and upgrading
compared to MTJ, the electrolyzer capacity is about 16% higher for FT. This difference
can explain the allowed increased costs of MTJ. A reversed effect that strengthens this
hypothesis can be observed Figure 15 if is compared to Figure 17. With reduced electricity
costs, its general share of the total costs is decreasing. This effect leads to a smaller allowed
operating window of MTJ compared to FT.

5. Conclusions
This work presented a superstructure optimization study of an integrated biorefinery
and Power-to-X process to produce liquid fuels, with a focus on jet fuel. Unlike other
superstructure optimization studies, it includes a wide range of electricity- and biomass-
based processes and allows a deep integration to benefit from synergy effects.
The Open sUperstrucTure moDeling and OptimizatiOn fRamework (OUTDOOR)
was utilized for modeling and optimization. It was improved for novel functionalities such
as advanced mass balances, which allow flexible mass integration between PtX and BtX
concepts. Furthermore, a screening algorithm to handle uncertain input data—as they often
emerge with novel processes—is incorporated. The results indicate that a coupled algae
biorefinery and methanol-to-jet based production of jet fuel is economic superior to stand-
alone BtX or PtX processes for a wide range of algae production costs and MTJ processing
costs. While this work presented a coupling of BtX to the methanol route as superior to the
Fischer–Tropsch route for a wide range of MTJ processing costs, it is important to notice that
MTJ as well as FT processes can be designed in various ways, utilizing differing process
selection, reaction conditions or catalysts. This variety also leads to diverse performances
in terms of efficiencies and costs. Therefore, the study at hand should not be seen as
a general ranking. Furthermore, the detailed design and engineering of such plants is
always highly dependent on the boundary conditions. The increased freshwater demand
of the cost-optimal PBtX plant, on the other hand, may be unproblematic for regions with
water abundancy; this would be different for water-scarce countries, e.g., Spain, which in
turn may have higher solar radiation and thus increased algae growth rates. Moreover,
electricity prices as well as used algae strains (saline vs. fresh water) influence the decision
on the technology choice. In the end, the complexity of integrated PBtX plant has to
be considered. Nonetheless, to meet the decided targets on greenhouse gas reductions,
different alternatives for renewable refineries have to be explored, and integrated concepts
should not be discarded directly due to potential economic and environmental benefits.
In the end, renewable processes have to be designed which meet the different criteria of
sustainability while still being flexible enough to react on changing feedstock availability
and product demand. Here, the presented framework, methodology and case study provide
a promising first start.

Supplementary Materials: The following are available online at https://www.mdpi.com/article/10

.3390/pr10071298/s1, Supplementary Information S1; Supplementary Information S2 [43–45,48–51].
Author Contributions: Conceptualization, P.K.; methodology, P.K.; software, P.K.; validation, P.K.
and T.W.; formal analysis, P.K.; investigation, P.K.; data curation, P.K.; writing—original draft
preparation, P.K.; writing—review and editing, T.W. and E.Z.; visualization, P.K.; supervision, E.Z.;
project administration, T.W.; funding acquisition, T.W. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was funded by the German Federal Ministry for Economic Affairs and
Climate Action within the KEROSyN100 project (funding code 03EIV051A).
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or
in the decision to publish the results.
Processes 2022, 10, 1298 27 of 30

Appendix A

Table A1. List of unit-operations of the renewable refinery superstructure as well as their model
data source.

Abbreviation Unit-Operation Data Source

LT-DAC Low temperature direct air capture [52]
OXY Oxyfuel fired cement factory [16,17]
CPU Cooling and purification of oxyfuel cement factory flue gases [16,17]
AEL Low pressure alkaline electrolyzer at 1 bar [19,20]
HP-AEL High-pressure alkaline electrolyzer at 30 bar [19,20]
HP-PEMEL High-pressure polymer electrolyte membrane electrolyzer at 30 bar [19,20]
SOEL Solid oxide electrolyzer at 1 bar [21]
ATR-SEL Selexol-based CO2 capture plant for ATR SynFeed Simulation, [31]
TRIR-SEL Selexol-based CO2 capture plant for TRIR SynFeed Simulation, [31]
Hydrogen pressure swing adsorption for H2 separation from
H2 -PSA Simulation, [31,53]
SMR SynFeed
BG-PSA Biogas pressure swing adsorption for CO2 separation [7]
VP Vacuum pump [7]
H2 -LH-COMP H2 compressor from low (1 bar) to high (70 bar) pressure Simulation, [18]
SMR-COMP Compressor for raw SynFeed from SMR to 70 bar Simulation, [31]
ATR-COMP Compressor for raw SynFeed from ATR to 70 bar Simulation, [31]
MeOH SYN Methanol synthesis unit [18]
MeOH FLASH Purge gas flash [18]
MeOH DC Methanol distillation column for water separation [18]
HEAT GEN Heat furnace to produce superheated steam [7]
EL GEN Combined gas- and steam turbine to produce electricity [7]
WWT Wastewater treatment plant [3]
SMR Steam methane reforming unit Simulation, [31]
ATR Autothermal reforming unit Simulation, [31]
TRIR Tri-reforming unit (for raw biogas) Simulation, [31]
MEA-CC Amine scrubbing-based carbon capture from flue gases [18]
CO2 -COMP CO2 compressor to 70 bar [18]
H2 -MH-COMP H2 compressor from medium (30 bar) to high (70 bar) pressure Simulation, [18]
SYNFEED COMP Compressor for SynFeed with molar H2 /CO2 ratio of 3 Simulation, [31]
H2O-DIST Purified water distributor –
O2-DIST Oxygen distributor –
CH4-DIST Bio-methane distributor –
ATR-DIST ATR-SynFeed distributor –
TRIR-DIST TRIR-SynFeed distributor –
SMR-DIST SMR-SynFeed distributor –
H2-DIST Hydrogen by-product distributor –
H2-LM-COMP H2 compressor from low (1 bar) to medium (30 bar) pressure Simulation, [18]
SONIC Sonication algae pretreatment [7]
HEX-EXT Hexane-based lipids extraction [7]
SUP-CO2 -EXT Supercritical CO2 -based lipid extraction [7]
BIO-U Bio-oil upgrading [2]
CENTR Centrifugation [7]
AAD Anaerobic digestion [7]
CENTR-DIST Centrifugation water distributor –
MTJ Methanol-to-Jet [14]
FT-M Fischer–Tropsch synthesis mixer [15]
RWGS Reverse water gas shift [15]
FT-R Fischer–Tropsch reactor [15]
FT-DC Fischer–Tropsch distillation column [15]
HYDRO Fischer–Tropsch hydrocracker [15]
FT-B Fischer–Tropsch burner [15]
 MTJ Methanol-to-Jet [14]
FT-M Fischer–Tropsch synthesis mixer [15]
RWGS Reverse water gas shift [15]
FT-R Fischer–Tropsch reactor [15]
FT-DC
Processes 2022, 10, 1298 Fischer–Tropsch distillation column [15] 28 of 30
HYDRO Fischer–Tropsch hydrocracker [15]
FT-B Fischer–Tropsch burner [15]

Processes 2022, 10, x FOR PEER REVIEW 30 of 34

Figure A1. Superstructure representation of renewable refinery for fuels production.
Figure A1. Superstructure representation of renewable refinery for fuels production.

Appendix B
Appendix B

External solver

create object / call solve function /

connect to return solved model instance
create object get results /
Superstructure SuperstructureModel provide analysis function
get instance Problem
BasicModel
create object / ModelOutput
Analyzer
provide connect to Superstructure
case study
«interface» data file Superstructure Optimizer create object / BasicMulti
Superstructure
Python API Model (Library) store results in object ModelAnalyzer
provide
prepare data file
exchange data /
create objects /

model instance
set input data

MultiModel get results /

User data input Output provide analysis function

AdvancedMulti
«interface» Unit-Operation ModelAnalyzer
Excel-Wrapper (Library)

Utility functions
provide utility function provide utility function
e.g. CAPEX linearizer e.g. model instance modifier

OUTDOOR core
Figure B1. Representation of OUTDOOR software architecture.
Figure A2. Representation of OUTDOOR software architecture.
Processes 2022, 10, 1298 29 of 30

References
1. Zondervan, E.; Nawaz, M.; de Haan, A.B.; Woodley, J.M.; Gani, R. Optimal design of a multi-product biorefinery system. Comput.
Chem. Eng. 2011, 35, 1752–1766. [CrossRef]
2. Klein-Marcuschamer, D.; Turner, C.; Allen, M.; Gray, P.; Dietzgen, R.G.; Gresshoff, P.M.; Hankamer, B.; Heimann, K.; Scott, P.T.;
Stephens, E.; et al. Technoeconomic analysis of renewable aviation fuel from microalgae, Pongamia pinnata, and sugarcane.
Biofuels Bioprod. Biorefining 2013, 7, 416–428. [CrossRef]
3. Albrecht, F.G.; König, D.H.; Baucks, N.; Dietrich, R. A standardized methodology for the techno-economic evaluation of
alternative fuels—A case study. Fuel 2017, 194, 511–526. [CrossRef]
4. Bertran, M.O.; Frauzem, R.; Sanchez-Arcilla, A.S.; Zhang, L.; Woodley, J.M.; Gani, R. A generic methodology for processing route
synthesis and design based on superstructure optimization. Comput. Chem. Eng. 2017, 106, 892–910. [CrossRef]
5. Yeomans, H.; Grossmann, I.E. A systematic modeling framework of superstructure optimization in process synthesis. Comput.
Chem. Eng. 1999, 23, 709–731. [CrossRef]
6. Quaglia, A.; Gargalo, C.L.; Chairakwongsa, S.; Sin, G.; Gani, R. Systematic network synthesis and design: Problem formulation,
superstructure generation, data management and solution. Comput. Chem. Eng. 2015, 72, 68–86. [CrossRef]
7. Gong, J.; You, F. Value-added chemicals from microalgae: Greener, more economical, or both? ACS Sustain. Chem. Eng. 2015,
3, 82–96. [CrossRef]
8. Galanopoulos, C.; Kenkel, P.; Zondervan, E. Superstructure optimization of an integrated algae biorefinery. Comput. Chem. Eng.
2019, 130, 106530. [CrossRef]
9. Onel, O.; Niziolek, A.M.; Elia, J.A.; Baliban, R.C.; Floudas, C.A. Biomass and natural gas to liquid transportation fuels and olefins
(BGTL+C2-C4): Process synthesis and global optimization. Ind. Eng. Chem. Res. 2015, 54, 359–385. [CrossRef]
10. Sánchez, A.; Castellano, E.; Martín, M.; Vega, P. Evaluating ammonia as green fuel for power generation: A thermo-chemical
perspective. Appl. Energy 2021, 293, 116956. [CrossRef]
11. Uebbing, J. Power-to-Methane Process Synthesis via Mixed Integer Nonlinear Programming. Ph.D. Thesis, Otto-von-Guericke-
Universität Magdeburg, Magdeburg, Germany, 5 July 2021.
12. Kenkel, P.; Wassermann, T.; Rose, C.; Zondervan, E. A generic superstructure modeling and optimization framework on the
example of bi-criteria Power-to-Methanol process design. Comput. Chem. Eng. 2021, 150, 107327. [CrossRef]
13. Schemme, S.; Breuer, J.L.; Köller, M.; Meschede, S.; Walman, F.; Samsun, R.C.; Peters, R.; Stolten, D. H2-based synthetic fuels:
A techno-economic comparison of alcohol, ether and hydrocarbon production. Int. J. Hydrogen Energy 2020, 45, 5395–5414.
[CrossRef]
14. Von Liebner, W.; Wagner, M. MtSynfuels® , die effiziente und wirtschaftliche Alternative zu Fischer-Tropsch-Treibstoffen. Erdoel
Erdgas Kohle 2004, 120, 323–326.
15. König, D.H. Techno-Ökonomische Prozessbewertung der Herstellung Synthetischen Flugturbinentreibstoffes aus CO2 und H2 .
Ph.D. Thesis, Uversität Stuttgart, Stuttgart, Germany, 30 November 2016.
16. Voldsund, M.; Gardarsdottir, S.O.; De Lena, E.; Pérez-Calvo, J.F.; Jamali, A.; Berstad, D.; Fu, C.; Romano, M.; Roussanaly, S.;
Anantharaman, R.; et al. Comparison of technologies for CO2 capture from cement production—Part 1: Technical evaluation.
Energies 2019, 12, 559. [CrossRef]
17. Gardarsdottir, S.O.; De Lena, E.; Romano, M.; Roussanaly, S.; Voldsund, M.; Pérez-Calvo, J.F.; Berstad, D.; Fu, C.; Anantharaman, R.;
Sutter, D.; et al. Comparison of technologies for CO2 capture from cement production—Part 2: Cost analysis. Energies 2019, 12, 542.
[CrossRef]
18. Wassermann, T.; Schnuelle, C.; Kenkel, P.; Zondervan, E. Power-to-Methanol at Refineries as a Precursor to Green Jet Fuel
Production: A Simulation and Assessment Study. In Proceedings of the Computer Aided Chemical Engineering; Elsevier: Amsterdam,
The Netherlands, 2020; Volume 48, pp. 1453–1458.
19. Proost, J. State-of-the art CAPEX data for water electrolysers, and their impact on renewable hydrogen price settings. Int. J.
Hydrogen Energy 2019, 44, 4406–4413. [CrossRef]
20. Smolinka, T.; Wiebe, N.; Sterchele, P.; Palzer, A.; Lehner, F.; Jansen, M.; Kiemel, S.; Miehe, R.; Wahren, S.; Zimmermann, F.
Industrialisierung der Wasserelektrolyse in Deutschland: Chancen und Herausforderungen für nachhaltigen Wasserstoff für Verkehr;
Bundesministerium für Verkehr und digitale Infrastruktur: Berlin, Germany, 2018.
21. Wang, L.; Chen, M.; Küngas, R.; Lin, T.E.; Diethelm, S.; Maréchal, F.; Van herle, J. Power-to-fuels via solid-oxide electrolyzer:
Operating window and techno-economics. Renew. Sustain. Energy Rev. 2019, 110, 174–187. [CrossRef]
22. Davis, R.; Markham, J.; Kinchin, C.; Grundl, N.; Tan, E.; Humbird, D. Process Design and Economics for the Production of Algal
Biomass: Algal Biomass Production in Open Pond Systems and Processing Through Dewatering for Downstream Conversion; National
Renewable Energy Laboratory: Golden, CO, USA, 2016.
23. Lorenzen, J.; Igl, N.; Tippelt, M.; Stege, A.; Qoura, F.; Sohling, U.; Brück, T. Extraction of microalgae derived lipids with
supercritical carbon dioxide in an industrial relevant pilot plant. Bioprocess Biosyst. Eng. 2017, 40, 911–918. [CrossRef]
24. Apel, A.C.; Pfaffinger, C.E.; Basedahl, N.; Mittwollen, N.; Göbel, J.; Sauter, J.; Brück, T.; Weuster-Botz, D. Open thin-layer cascade
reactors for saline microalgae production evaluated in a physically simulated Mediterranean summer climate. Algal Res. 2017,
25, 381–390. [CrossRef]
25. Fernández, F.A.; Sevilla, J.M.F.; Grima, E.M. Cost analysis of microalgae production. In Biofuels from Algae; Elsevier: Amsterdam,
The Netherlands, 2019; pp. 551–566.
Processes 2022, 10, 1298 30 of 30

26. Chisti, Y. Biodiesel from microalgae. Biotechnol. Adv. 2007, 25, 294–306. [CrossRef]
27. Davis, R.; Aden, A.; Pienkos, P.T. Techno-economic analysis of autotrophic microalgae for fuel production. Appl. Energy 2011,
88, 3524–3531. [CrossRef]
28. Uduman, N.; Qi, Y.; Danquah, M.K.; Forde, G.M.; Hoadley, A. Dewatering of microalgal cultures: A major bottleneck to
algae-based fuels. J. Renew. Sustain. Energy 2010, 2, 12701. [CrossRef]
29. Iglina, T.; Iglin, P.; Pashchenko, D. Industrial CO2 Capture by Algae: A Review and Recent Advances. Sustainability 2022, 14, 3801.
[CrossRef]
30. Kamperidou, V.; Terzopoulou, P. Anaerobic digestion of lignocellulosic waste materials. Sustainability 2021, 13, 12810. [CrossRef]
31. Kenkel, P.; Wassermann, T.; Zondervan, E. Biogas Reforming as a Precursor for Integrated Algae Biorefineries: Simulation and
Techno-Economic Analysis. Processes 2021, 9, 1348. [CrossRef]
32. Capra, F.; Magli, F.; Gatti, M. Biomethane liquefaction: A systematic comparative analysis of refrigeration technologies. Appl.
Therm. Eng. 2019, 158, 113815. [CrossRef]
33. Wassermann, T.; Mühlenbrock, H.; Kenkel, P.; Thöming, J.; Zondervan, E. Optimization of hydrogen supply from renewable
electricity including cavern storage. Phys. Sci. Rev. 2022; submitted. [CrossRef]
34. Wernet, G.; Bauer, C.; Steubing, B.; Reinhard, J.; Moreno-Ruiz, E.; Weidema, B. The ecoinvent database version 3 (part I): Overview
and methodology. Int. J. Life Cycle Assess. 2016, 3, 1218–1230. [CrossRef]
35. Fraunhofer ISE. Stromgestehungskosten Erneuerbare Energien; Fraunhofer ISE: Freiburg, Germany, 2021.
36. Methanex. Durchschnittlicher Preis für Methanol auf dem europäischen Markt in den Jahren von 2012 bis 2019 (in Euro je Tonne).
Available online: https://de.statista.com/statistik/daten/studie/ (accessed on 26 November 2019).
37. Turton, R.; Bailie, R.C.; Whiting, W.B. Analysis, Synthesis, and Design of Chemical Processes; Pearson Education: Upper Saddle Creek,
NJ, USA; Volume 36, ISBN 9780132618120.
38. Umweltbundesamt. Optionen für Biogas-Bestandanlagen bis 2030 aus Ökonomischer und Energiewirtschaftlicher Sicht; Umwelt
Bundesamt: Dessau-Roßlau, Germany, 2020.
39. Langhoff, W. MWV—Jahresbericht 2020. 2020. Available online: https://en2x.de/wp-content/uploads/2021/11/MWV_
Mineraloelwirtschaftsverband-e.V.-Jahresbericht-2020.pdf (accessed on 5 May 2022).
40. IATA. Jet Fuel Price Monitor. Available online: https://www.iata.org/en/publications/economics/fuel-monitor/ (accessed on
15 January 2022).
41. Wirtschaftsverband Fuels und Energie e.V. Verbraucherpreise. Available online: https://en2x.de/service/statistiken/
verbraucherpreise/ (accessed on 5 May 2022).
42. Kenkel, P.; Wassermann, T.; Rose, C.; Zondervan, E. Outdoor–An open-source superstructure construction and optimization tool.
In Computer Aided Chemical Engineering; Elsevier: Amsterdam, The Netherlands, 2021; Volume 50, pp. 413–418.
43. Kong, Q.; Shah, N. Development of an Optimization-Based Framework for Simultaneous Process Synthesis and Heat Integration.
Ind. Eng. Chem. Res. 2017, 56, 5000–5013. [CrossRef]
44. Yee, T.F.; Grossmann, I.E. Simultaneous optimization models for heat integration-II. Heat exchanger network synthesis. Comput.
Chem. Eng. 1990, 14, 1165–1184. [CrossRef]
45. Ciric, A.R.; Floudas, C.A. Heat exchanger network synthesis without decomposition. Comput. Chem. Eng. 1991, 15, 385–396.
[CrossRef]
46. Bisshop, J. AIMMS: Optimization Modelling; AIMMS: Boca Raton, FL, USA, 2016.
47. Wassermann, T.; Muehlenbrock, H.; Kenkel, P.; Zondervan, E. Supply chain optimization for electricity-based jet fuel: The case
study Germany. Appl. Energy 2022, 307, 117683. [CrossRef]
48. Bisschop, J. AIMMS Modeling Guide-Integer Programming Tricks. 2016. Available online: https://download.aimms.com/
aimms/download/manuals/AIMMS3OM_IntegerProgrammingTricks.pdf (accessed on 26 November 2019).
49. Morrison, R. SOS2 Constraints in GLPK. Available online: https://www.scribd.com/document/73901813/glpk-sos2-02
(accessed on 26 November 2019).
50. Peters, M.S.; Timmerhaus, K.D.; West, R.E. Plant Design and Economics for Chemical Engineers, 5th ed.; Glandt, E.D., Klein, M.T.,
Edgar, T.F., Eds.; McGraw-Hill: New York, NY, USA, 2003.
51. Horne, R.; Grant, T.; Verghese, K. Life Cycle Assessment: principles, Practice, and Prospects; Csiro Publishing: Clayton, Australia, 2009.
52. Fasihi, M.; Efimova, O.; Breyer, C. Techno-economic assessment of CO2 direct air capture plants. J. Clean. Prod. 2019, 224, 957–980.
[CrossRef]
53. Spallina, V.; Pandolfo, D.; Battistella, A.; Romano, M.C.; Van Sint Annaland, M.; Gallucci, F. Techno-economic assessment of
membrane assisted fluidized bed reactors for pure H2 production with CO2 capture. Energy Convers. Manag. 2016, 120, 257–273.
[CrossRef]