Biomass and Bioenergy 150 (2021) 106142

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Biomass and Bioenergy

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

Research paper

Process simulation and techno-economic assessment of Salicornia sp. based

jet fuel refinery through Hermetia illucens sugars-to-lipids conversion and
HEFA route
Malthe Fredsgaard ∗, Laura Sini Sofia Hulkko, Tanmay Chaturvedi, Mette Hedegaard Thomsen
Department of Energy Technology; Aalborg University, Niels Bohrs Vej 8, 6700 Esbjerg, Denmark

ARTICLE INFO ABSTRACT

Keywords: Succulent halophyte Salicornia sp. was characterized to evaluate its suitability for biorefinery, as soil salin-
Halophyte ization is seen as a major agricultural issue and the demand for biofuel is increasing. Green fractionation of
Salicornia sp. biomass approach was chosen, with liquid and solid fractions of the biomass considered separately. Soxhlet
HEFA-SPK
extractions were used to separate different biochemical groups from the pulp, and the lignocellulosic residue
Hermetia illucens
was hydrothermally pretreated, enzymatically hydrolyzed, mixed with an existing agricultural feedstock,
SuperPro Designer
and fed to black soldier fly larvae (BSFL) for sugars-to-lipids conversion. The ASTM approved route of
hydroprocessed esters and fatty acids (HEFA) was applied using in silico study of processing BSFL lipids to
sustainable jet fuel, using SuperPro Designer and Aspen HYSYS. Simulations and techno-economic assessment
showed, with the applied process routes, inputs and production rates, the biorefinery process will be profitable
in 7 years, with a biomass input flow rate of over 60 ton h−1 Salicornia sp. with decreasing payback time as the
biomass input flow rate increases. Therefore, Salicornia sp. feedstock and sugars-to-lipids conversion method
for biorefinery and liquid fuel production can function as a feasible biorefinery process with a normalized
CO2 -e reduction of HEFA-SPK of 95.5% compared to similar fossil fuels.

1. Introduction Acids-Synthetic Paraffinic Kerosene (HEFA-SPK) to be the cheapest bio-

jet fuel to produce, even when changing the lipid feedstock input of the
An increase in public climate awareness has pushed the European biorefinery simulation [4]. Multiple lipid feedstocks are available for
Union (EU) to set aviation sustainability goals for 2050 with a 75% oil to jet fuel conversion, as oils and paraffins are similar in molecular
reduction in CO2 emissions per passenger kilometer, a 90% reduction structure to alkanes in the jet fuel range. As jet fuel comprises of alkanes
in total NO𝑥 emissions, and a 65% noise reduction compared to a in the range of 8 to 16 carbon atoms per molecule, free fatty acids
typical new aircraft of the year 2000 [1]. These emission reduction (FFA) from depropanation of oils, and paraffins with slightly higher
goals are ambitious, as the yearly passenger-kilometers will rapidly molecule lengths, are ideal feedstocks for HEFA-SPK production [5].
increase the aviation carbon footprint, if conventional fossil fuels are Fuel properties of jet fuel, such as freezing point temperature, kinematic
being used [2]. To reach the said goals, the production capacity of viscosity, and density, are strictly specified by ASTM to ensure high
sustainable jet fuels has to be increased all over the world, as the
quality and a dependable fuel, which again is determined by refining
share of sustainable aviation fuel in 2019 in the fuel aviation fuel
conditions. A difference in refining conditions will show differences
blend was 0.05 w%, and increasing this share above 2 w% requires
in alkane length, isomerization, carbon-to-hydrogen ratio, and thereby
research in new conversion methods apart from what has already
fuel properties. Especially isomerization of n-alkanes in the HEFA-SPK
been researched [3]. Biofuels can be made from excess 2nd generation
process route is crucial, as isomerization will lower the freezing point
biomass, which would otherwise be considered biowaste, hence not
temperature, and alter other thermodynamical properties to resemble
compete with food production. To make use of this excess biomass, it
has to be processed into a usable biorefinery feedstock and preferably the commonly used jet fuel, Jet A-1 [6].
not compete with human food production, e.g. vegetable oil produc- Living organisms have developed digestion systems suitable for
tion. Bann et al. in 2016 compared the financial potential for different various kinds of substrates, and in recent years, the interest of using in-
biofuel refinery processes, and found Hydroprocessed Esters and Fatty sect digestion for lignocellulosic biomass conversion has increased [7].

∗ Corresponding author.
E-mail address: [email protected] (M. Fredsgaard).

https://doi.org/10.1016/j.biombioe.2021.106142
Received 4 January 2021; Received in revised form 19 May 2021; Accepted 23 May 2021
Available online 31 May 2021
0961-9534/© 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

Hermetia illucens, commonly known as black soldier fly larva (BSFL), survival and reproductive rate in saline conditions, were chosen to be
can be used as a novel bio-waste treatment to convert organic waste, simultaneously added to the juice, for an in situ lactic acid-producing
such as manure, fruit, or vegetable waste, into high protein and high bacteria cultivation.
lipid animal feed [8,9]. Trends show insect-based animal feeds can Laboratory scale extractions of lipids, secondary metabolites, salts,
be produced in a more sustainable way than conventional feed crops, and other organic material were performed using the Soxhlet extraction
partly because of the large array of feeds the BSFL can digest [10]. method [17]. Lipids were extracted using n-hexane, and a sequential
Using BSFL is an easy, cheap, and scalable bio-waste treatment from extraction using ethanol (EtOH) extracted secondary metabolites, salts,
biomass to lipids and valuable compounds, such as protein, organic and other organic compounds. Salt removal by Soxhlet EtOH extraction
fertilizer, and chitin [10]. The annual halophyte Salicornia sp. is used was verified post extractions using a protocol developed by the National
worldwide as a gourmet vegetable, but after the growing period, the Renewable Energy Laboratory (NREL) for ashing, which showed a
biomass lignifies, and cannot be used for food production. This resid- 100 w% removal of ashes [18]. Extractions were performed using 7–
ual biomass has great potential for phytochemical extractions, as the 10 g dried and milled Salicornia sp. to 150 ml solvent, and weighed
plant contains large amounts of antioxidants with great medicinal before, between, and after each extraction to determine the mass of
properties [9,11–14]. Approximately 17,300 kg ha−1 yr−1 lignified the extracts. The weighing was performed after solvent evaporation
Salicornia persica has been reported to be left over after cultivation at and drying of the biomass and Soxhlet thimbles. The extracted lipids
optimal conditions, and shows to be a large problem for the halophyte from Salicornia sp. are expected to have a high nutritional value, as
farmers, as the biomass contains high concentrations of salts, making similar species of Salicornia spp. show to have content of healthy
incineration or composting impractical. Furthermore the cultivation polyunsaturated fatty acids [19,20]. Total nitrogen was determined
of Salicornia sp. can happen on salt affected lands, and due to its with modified Dumas combustion method, and crude protein was
bioremediation properties, it will be capable of decreasing salt content approximated with a 6.0 conversion factor, as a higher conversion
in soil [15,16]. In this study, Salicornia sp. found in the Wadden factor of 6.25 tend to overestimate the protein content [21,22]. Sugars
Sea area of northern Europe, will be fractionated and processed into and lignin in lignocellulose were determined by strong acid hydrolysis
value-added streams and a lignocellulosic waste product. This waste followed by ashing of the remaining non-acid soluble material and
product will be converted into lipids and high-value co-products, and high-performance liquid chromatography (HPLC) analysis. For further
further refined into biofuels. Thus, the idea of circular economy will be details on characterization done on Salicornia sp. before SPD simula-
implemented to use all possible components of the feedstock, and seen tion, the authors refer to the work done by Hulkko and Fredsgaard
as a route for sustainable and feasible production of 2nd generation (manuscript in preparation).
biomass to fuel.
2.2. Hermetia illucens characterization
2. Materials and methods
In cooperation with Enorm Biofactory A/S feed trials on BSFL have
Biomass characterization experiments, mass balances and a simula-
been made. The trials were 100 w% chicken feed (CF) and 60/40 w%
tion from biomass to HEFA-SPK and value-added components, as shown
CF and extractive free Salicornia sp. respectively. The feedstocks had
by process overview in Fig. 1, were made to determine the biofuel yield
a dry matter (DM) content of 30 w% with a feed mass of 1150 g.
and feasibility by a techno-economic assessment (TEA) using Intelligen
After a growing period of 14 days, the larvae were separated from
SuperPro Designer (SPD). Salicornia sp. was simulated as a biorefinery
the remaining feed and frass and devitalized using steam. The larvae
feedstock, extracted crude high-value secondary metabolites, and ex-
were dried using a 50 ◦ C forced ventilation oven for 48 h. The lipid
cess lignocellulosic biomass underwent hydrothermal pretreatment to
content of the BSFL was determined by the Soxhlet extraction method
break the lignocellulosic structure for cellulase to hydrolyze the cellu-
using n-hexane [17]. Large scale data regarding phase separation of the
lose into glucose. This pretreated slurry was simulated to be fermented
solid and liquid phase of the BSFL by 50 ◦ C heated screw press, protein
for BSFL to digest using a lactic acid-producing bacteria culture, and
content, and water content were given by Enorm Biofactory A/S [23].
BSFL was fractionated into fractions of lipids, protein, a solid residue
Feed trials using pretreated and hydrolyzed extractive free Salicornia
containing chitin, and aqueous waste products. The BSFL lipids were
sp. have not been made, and BSFL composition data for simulation is
hydrogenated, hydrocracked and isomerized. Fuels in the molecular
based on intermediate characterization values of 100 w% CF and 60/40
range of gasoline, Jet A-1 and diesel, hereon referred to as naphtha,
w% CF and extractive-free Salicornia sp. respectively.
HEFA-SPK, hydrogenated vegetable oil (HVO) respectively, and alkane
flash products were produced.
Modeling methods
Experimental work for modeling inputs
Each subsection will refer to one or more numbers on Fig. 1 for a
2.1. Salicornia sp. biomass characterization better process overview.

Data inputs for the Salicornia sp. biorefining simulation were all 2.3. Salicornia sp. biorefining simulation (1–4)
obtained through laboratory scale experiments, done on the biomass
sampled 11th November 2019. For the biochemical characterization The Salicornia sp. biorefining simulation is split up into four over-
of the primary metabolites of Salicornia sp., the halophytic biomass all steps: preprocessing, n-hexane Soxhlet extraction, EtOH Soxhlet
was sampled from the Danish Wadden sea national park, coordinates: extraction, and pretreatment/enzymatic hydrolysis.
55.307733,8.652292, on 15th October 2019 and 11th November 2019. Preprocessing of the biomass consisted of an initial green frac-
Characterization of the primary metabolites was done on the biomass tionation into pulp and juice by screw pressing. After screw pressing,
sampled 15th October 2019, and BSFL feed trials were done using the the remaining water was evaporated off, and the dried biomass was
biomass sampled 11th November. The biomass was rinsed using tap shredded.
water, fractionated into a solid (pulp) and liquid (juice) fraction using After shredding, the biomass was transported to the first of two
a domestic single horizontal auger screw press (Omega EUJ-707, Sana, Soxhlet extractions. As SPD does not have a Soxhlet extraction unit, the
Czech Republic). The pulp was dried in a 50 ◦ C forced ventilation extraction was modeled using relevant sub-components. The modeled
oven and milled using a knife mill (GM200, Retsch, Germany) at Soxhlet cycle was simulated as a semi-continuous reaction, as the new
10,000 rpm for 45 s. Suitable lactic acid-producing bacteria, with high solvent continuously entered the extractor unit, but the solids were

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M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

Fig. 1. Full schematic overview of the process presented in this paper. Diamond figures are process equipment or sub-processes, rectangular figures are material, dark blue rectangles
are products and co-products. SuperPro Designer simulation layout can be seen in Figs. 7 to 15. Section 1: Preprocessing of Salicornia sp. Section 2: N-hexane Soxhlet extraction.
Section 3: Ethanol Soxhlet extraction. Section 4: Hydrothermal pretreatment and enzymatic hydrolysis of extractive free lignocellulosic Salicornia sp. Section 5: Lactiplantibacillus
plantarum cultivation in Salicornia sp. juice. Section 6: BSFL feedstock fermentation and BSFL cultivation. Section 7: BSFL processing. Section 8: BSFL lipid hydrodeoxygenation
and hydrocracking and isomerization. Section 9: Fuel distillation. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)

suspended in the extraction unit with a retention time of 1 h for n-

Table 1
hexane extraction and 6 h for EtOH extraction. The cycle consisted Enzyme calculation data.
of a continuous storage unit (Soxhlet extraction chamber), evapora- Parameter Symbol Value Unit
tion unit, using low-pressure mechanical vapor recompression (Soxhlet Mass flow, cellulose 𝑚̇ 𝑐𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒 100 kg h−1
siphon), custom mixing make-up valve (continuously added solvent), Activity FPU𝑙𝑜𝑎𝑑𝑖𝑛𝑔 15 FPU g−1
and solvent buffer tank (round bottom flask). The low-pressure stream Activity FPU𝑏𝑎𝑡𝑐ℎ 75 FPU mL−1
was recondensed by compression after the evaporation unit to ensure Density 𝜌𝑐𝑒𝑙𝑙𝑢𝑙𝑎𝑠𝑒 1.2 g mL−1
Mass flow, enzyme 𝑚̇ 𝑐𝑒𝑙𝑙𝑢𝑙𝑎𝑠𝑒 31.2 kg h−1
a liquid phase, hence there would be no phase change inside the
rotational machinery that would cause equipment damage. The evapo-
rator unit would recycle 99 w% of the solvent, which was the default
value provided by SPD. 99 w% of the remaining solvent and solvent of the feedstock for insect consumption. Using data from literature [24–
solubles got decanted off and stored in a storage unit. To provide a 28] and the value for cellulose of 24.5 g/100 gDM obtained from
pure concentrate of the extracted compounds, the solvents would get previous characterization work done by the authors, the amount of
fully vented off in the storage unit, and recycled back into the Soxhlet cellulase added to the hydrothermally pretreated slurry was calculated
extraction cycle. The overall recycling of the solvent is therefore 99.99 as described in Eq. (1), where 𝑚̇ 𝑐𝑒𝑙𝑙𝑢𝑙𝑎𝑠𝑒 is the mean mass flow rate of
w%, and the remaining solvent would evaporate off during biomass cellulase provided to the batch enzymatic hydrolysis reactor, 𝑚̇ 𝑐𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒 is
transportation. the mean mass flow rate of cellulose of the slurry provided to the batch
The extractive free biomass, consisting of lignocellulose and dena- enzymatic hydrolysis reactor, FPU𝑙𝑜𝑎𝑑𝑖𝑛𝑔 is the filter paper activity per
tured protein, was simulated to be pretreated as described by Alassali unit mass of lignocellulosic DM, FPU𝑏𝑎𝑡𝑐ℎ is the filter paper activity of
et al. on S. sinus-persica [24]. The optimal hydrothermal pretreat- the batch of enzymes per mL, 𝜌𝑐𝑒𝑙𝑙𝑢𝑙𝑎𝑠𝑒 is the density of cellulase and
ment conditions, followed by fermentation, for highest EtOH yield was 76.9 % is the conversion from the paper of Alassali et al. [24].
shown to be 170 ◦ C for 10 min with a conversion of 76.9%. As the
biomass was used as feedstock, the chosen hydrolysis method was 𝑚̇ 𝑐𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒 ⋅ 𝐹 𝑃 𝑈𝑙𝑜𝑎𝑑𝑖𝑛𝑔 ⋅ 𝜌𝑐𝑒𝑙𝑙𝑢𝑙𝑎𝑠𝑒
𝑚̇ 𝑐𝑒𝑙𝑙𝑢𝑙𝑎𝑠𝑒 = (1)
enzymatic hydrolysis, as strong acid hydrolysis would affect the quality 𝐹 𝑃 𝑈𝑏𝑎𝑡𝑐ℎ ⋅ 76.9 %

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M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

The high mass ratio of cellulase to cellulose is based on laboratory 2.5. HEFA-SPK process simulation (8)
scale enzymatic hydrolysis for optimal performance, and is considered
to be very high for full-scale production. It should also be noted that The HEFA-SPK process route is a process with the input of lipids
the cellulase is suspended in a liquid, and is therefore a suspension and and hydrogen and output of n-alkanes, i-alkanes, propane, water and
not a pure enzyme mixture, hence the high enzyme concentration [28] CO and CO2 . This process was simulated in two reactors: hydrodeoxy-
(see Table 1). genation (HDO) reactor and hydrocracking and isomerization (HI) re-
actor. In each reactor, multiple parallel reactions occurred. In the HDO
packed bed reactor (PBR), the BSFL lipid underwent the following reac-
2.4. Hermetia illucens biorefining simulation (5–7) tions: hydrogenation of triglycerides, depropanation, decarboxylation
(DCO2 ), decarbonylation (DCO), synthesis of intermediate aldehyde
and alcohol products, and HDO of alcohol to n-alkane [6]. The lighter
As BSFL are hatched from fly eggs, an initial larvae culture needs to
gaseous products were separated by flash separation, and the liquid n-
be made. Enorm Biofactory A/S is doing this in simple fly-cages, where
alkanes were further processed in a HI reactor. The mixture of alkanes
the flies lay eggs in-between pieces of cardboard. This was simulated to
could then be distilled to yield naphtha, HEFA-SPK, and HVO with
happen continuously in a drum, with a small portion of the produced specified predetermined distillation temperatures.
prepupae larvae as input and fly eggs as output. Black soldier flies do
not need food as they are mating, but only an insignificant amount 2.5.1. Hydrogenation of triglycerides
of water [23]. In SPD, the cultivation of BSFL was simulated as a silo In the HEFA process route, the lipid feedstock often consists of a
with specific conditions and the residence time of 14 days. In reality, mixture of saturated, mono-unsaturated, and poly-unsaturated triglyc-
the cultivation is happening in separate parallel rooms with suitable erides. HEFA-processing unsaturated triglycerides would result in the
ambient conditions, and the larvae are laying in trays placed in racks formation of alkenes, with less desirable combustion characteristics,
to make the transferring easier. therefore the initial hydrogenation of unsaturated triglycerides was
After the cultivation of BSFL, the larvae and frass were simulated crucial. As the triglyceride profile of terrestrial animals is often higher
separated by a coarse screen. The frass was simulated stored in a big in saturated triglycerides than oil-producing crops, the saturation of
silo. A small amount, 1 w% of the total amount of cultivated BSFL, the unsaturated fatty acids from animal fat is less hydrogen inten-
was transferred into the drum to allow for pupation and lay eggs sive [31]. An example of saturation of cis-unsaturated triglyceride is the
saturation of monounsaturated triglyceride triolein (tri-C18:1) into the
to maintain the number of input larvae. The remaining BSFL were
saturated triglyceride, tristrearin (tri-C18:0). This process can be done
devitalized using steam and transported to a storage unit. The storage
at a temperature of 175 ◦ C and a pressure of 0.55 MPa with nickel as
unit was needed as the cultivation of BSFL was batch cultivation, and
a catalyst [32].
intermediate storage would allow for a continuous output flow rate.
Reaction 1:
From the storage unit, the BSFL were pressed using a hot screw press.
Cn H(2n−1−6m) (COOH)3 + (3 m)H2
Given by data from Enorm Biofactory A/S, the screw press separates
Ni
the liquid phase containing lipids, water, and protein from the solid ⟶ Cn H(2n−1) (COOH)3
phase containing the BSFL exoskeleton and residual matter from the
where n is the number of carbon atoms in the triglyceride aliphatic
BSFL. The exoskeleton was high in chitin and could be sold as a value-
chain, m is the number of double bonds in each aliphatic chain.
added product. After screw pressing, the lipid and water phases were
The conversion factor for saturation of tri-C18:1 can be found by the
separated. Solid protein was separated from the water, dried, and sold research of Swicklik et al. and a reaction rate constant can be calcu-
as a value-added product. lated [32]. As the difference in molecular structure between long-chain
triglycerides is not considered to be big, all unsaturated triglycerides
are simulated to react at the same rate.
2.4.1. In situ lactic acid-producing bacteria production
Feeding of BSFL typically lasts 14 days, hence the feedstock was
2.5.2. Depropanation
required to stay fresh for a period of 14 days and the growth of Triglycerides comprise of a glycerin backbone and three fatty acid
mold should be inhibited. To ensure a feedstock of high quality, a branches. These can be separated by a catalytic reaction using hydrogen
culture of lactic acid-producing bacteria was added to the feedstock as reactant, yielding propane and FFAs [33]. In the reaction equation of
to allow for lactic acid fermentation. In situ production of lactic acid- the depropanation of saturated triglycerides, n is the number of carbon
producing bacteria using Salicornia sp. juice was desired, as this would molecules in the FFAs. The used catalyst, nickel with molybdenum
lower the operation cost of the biorefinery, and utilize a waste stream. promoted aluminum oxide (Ni-Mo/Al2 O3 ), is described by Sinha et al.
Small scale feedstock trials done by Enorm Biofactory A/S used the in the review of HEFA processing [33].
Danish commercial dairy product A38 by Arla, containing Lactobacillus Reaction 2:
acidophilus in a ratio of 1:22 dairy product to feedstock. As Lactobacillus
acidophilus, used by Enorm Biofactory A/S, was salt-tolerant up to 5 g Cn H(2n−1) (COOH)3 + 3 H2
L−1 NaCl, the juice fraction from the initial screw pressing could not Ni−Mo/Al2 O3
be used as a culture medium for the in situ production of Lactobacillus ← 3 Cn H2n+1 COOH + C3 H8
←←←←←←←←←←←←←←←←←←←←←←←⟶
acidophilus [29]. The ashing results of Salicornia sp. juice showed the
juice contained an ash content of 11 g L−1 , with the majority of the ash
2.5.3. Hydrodeoxygenation
from the juice expected to be salt, as shown by the authors Hulkko and
To produce n-alkanes from the saturated FFAs, the carboxyl groups
Fredsgaard (manuscript in preparation). Lactiplantibacillus plantarum of FFA molecules needed to be removed and replaced with hydrogen,
(LBP), previously defined by the taxonomy Lactobacillus plantarum, or the oxygen removed in a HDO reactor. HDO is not a straight reaction
known for its high salt tolerance, was chosen to be simulated for in route, as some reaction intermediates will be produced. In a study by
situ lactic acid production. LBP has shown optimal growth up to 60 g Arora et al. [34] investigating the synthesis of octadecane (C18) from
L−1 NaCl and to be able to grow at pH 4–8 [30]. This made LBP an the FFA stearic acid (C18:0) using the catalyst Ni-Mo/Al2 O3 , reaction
ideal candidate for in situ production of lactic acid-producing bacteria, intermediates octadecanal (C18=0) and octadecanol (C18-OH) were
to be used in feedstock fermentation. found, with heptadecane (C17) being a by-product from direct DCO2

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M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

of C18:0 and decarbonylation of C18=O. These aldehyde and alcohol

Table 2
reaction intermediates, will further react with hydrogen to form C18, HI reactions defined in mass percentage as suggested by Martinez-Hernandez et al. [6].
as shown in Fig. 2. Martinez-Hernandez et al. determined by simulation Reaction yield [%]
in SPD the ratios of HDO, DCO2 and DCO to be 60.1 w%, 36.1 w% and
Reaction Reaction Reaction Reaction Reaction
3.8 w% respectively for palm oil [6]. Reaction 3–7 can be seen in Fig. 2. 8 9 10 11 12
C3 – – – – –
Ni−Mo/Al2 O3 C7 – – – – –
Reaction 3: C18∶0 + H2 ←←←←←←←←←←←←←←←←←←←←←←←⟶
← C18 = O + H2 O C8 – – – – 90
Ni−Mo/Al2 O3 C9 – – – – 88
Reaction 4: C18∶0 ←←←←←←←←←←←←←←←←←←←←←←←⟶
← C17 + CO2 C10 – – – – 90
Ni−Mo/Al2 O3 C11 – – – – 90
Reaction 5: C18 = O + H2 ←←←←←←←←←←←←←←←←←←←←←←←⟶
← C17 + CO C12 – – – – 90
Ni−Mo/Al2 O3 C13 5.8 – – – 90
Reaction 6: C18 = O + H2 ←←←←←←←←←←←←←←←←←←←←←←←⟶
← C18 − OH C14 61.7 – – – 53.9
Ni−Mo/Al2 O3 C15 51.3 – – – 27.2
Reaction 7: C18 − OH + H2 ←←←←←←←←←←←←←←←←←←←←←←←⟶
← C18 + H2 O C16 37.1 – – 18.0 6.0
C17 50.4 17.3 2.0 – 12.6
C18 4.9 41.9 13.9 23.2 18.9

2.6. Hydrocracking and isomerization (8)

Table 3
To make the fuel products meet the ASTM standards set for HEFA- Fuel limits for Jet A-1 as reported by Stark et al. [42].

SPK, the n-alkanes were hydrocracked and isomerized. This would Parameter Jet A-1 Unit

result in a lower freezing point of the fuel while maintaining high en- Density at 15 ◦ C 775–840 kg m−3
Max. sulfur content 0.3 w%
ergy released from combustion. The two reaction types, hydrocracking,
Max. total aromatics 26.5 vol%
and isomerization would happen simultaneously in a PBR, with the Max. T10 205 ◦
C
presence of free excess hydrogen. Hydrocracking is the reaction where Max. T90–T10 300 ◦
C
◦
long-chained alkanes are split into two smaller alkanes and saturated Max. final point >22 C
Max. freezing point ◦
with hydrogen to prevent the formation of alkenes. Isomerization is −47.0 C
Max. viscosity at −20 ◦ C 8.0 mm2 s−1
the reaction of rearranging the atoms in alkanes, for example, from Flash point 38.0 ◦C

n-decane to i-decane. Successful research has been done considering

HI of vegetable oils and non-edible oils and fats [35–39], but HI is
typically performed to fossil crude hydrocarbons, to satisfy the demand
for lighter hydrocarbon fractions [6]. 2.7. Distillation (9)
Studies of HI on n-alkanes in the range of C8–C18 were done by
Flinn et al. [40] and Coonradt et al. [41], and backed up by Martinez- Distillation was simulated using the Aspen HYSYS process design
Hernandez et al. [6], giving a set of possible reactions of HI, reaction tool, as SPD does not calculate complex azeotropic thermodynamic
properties of alkanes, which were necessary to know to comply with
8–12. It should be noted, the number of carbon atoms in the molecules
ASTM standards shown in Table 3. Distillation took place in two
of biofuel is similar to the number of carbon atoms, and general
separate columns, where the first column separates the HI alkanes in
structure, in the FFA chains of BSFL lipids [31]. All hydrocracking
the gasoline range, and the second column separates the jet fuel range
reactions were splitting alkanes into the range C8–C15, which has
from the diesel range.
molecules within the jet fuel range. This will happen simultaneously
After HI of the fuel, some gaseous C3 H8 , H2 O, H2 , CO, CO2 and other
with isomerization.
light alkanes, due to the azeotropic properties of the alkane mixture,
Hydrocracking would be flashed off to ensure a purer crude fuel. If these molecules
Reaction 8: were not flashed off, it would greatly affect the properties of especially
the distilled naphtha, and water would complicate distillation.
Cn H2n+2 + H2 ⟶ Cn−3 H2n−4 + C3 H8 for n = 13 − 18 For naphtha distillation, the heavy key simulation distillation tem-
perature, where the distilled molecule with the highest boiling point
Reaction 9:
would boil, was 190 ◦ C, which was the mean value of 175 ◦ C and
Cn H2n+2 + H2 ⟶ Cn−8 H2n−14 + C8 H18 for n = 17 − 18 205 ◦ C, as proposed by Leffler et al. [43]. This temperature was also
considered to be a reasonable light key distillation temperature of
Reaction 10: HEFA-SPK, where the distilled molecule with the lowest boiling point
will boil, of HEFA-SPK [42]. The heavy key temperature of 220 ◦ C
Cn H2n+2 + H2 ⟶ Cn−7 H2n−12 + C7 H16 for n = 17 − 18
is chosen, as Jet A-1 fuel range molecules, can be distilled in the
Reaction 11: temperatures of 175–315 ◦ C, but temperatures of 175–205 ◦ C and
300–315 ◦ C could yield unwanted physical properties for the jet fuel
Cn H2n+2 + H2 ⟶ 2 Cn∕2 Hn+2 for n = 16, 18 product [42]. The freezing point of HEFA-SPK was set as one of the
primary constraints in the distillation simulation in Aspen HYSYS.
Isomerization As the freezing point was not determined directly in Aspen HYSYS,
Reaction 12: it is calculated using Eq. (2) based on the data of freezing points
of n-alkanes, estimated freezing points of i-alkanes from Martinez-
Cn H2n+2 ⟶ iso − Cn H2n+2 for n = 6 − 18 Hernandez et al. [6], and the molar fractions of alkanes of the distilled
Reactions 8–11 occur simultaneously for C16–C18, followed by jet fuel stream (see Fig. 3).
reaction 8 for C13–C15, and finally all isomerization reactions occur.
As reactions 8–11 occurs simultaneously for C18, only 16.1 w% of the ∑
𝐶18
𝐹 𝑃𝐽 𝑒𝑡 𝐴−1 = 𝐹 𝑃𝑖 𝑦𝑖 (2)
initial C18 is left. Of that, isomerization occurs for 18.9 w%, leaving
𝑖=𝐶8
13.1 w% C18 in the final fuel, of the initial amount (see Table 2).

5
M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

Fig. 2. Possible reactions HDO, DCO2 and DCO reactions for C18:0.

Table 4
Operation and simulation parameters 1. All parameters determined by laboratory
work.
Parameter Value Unit
Preprocessing of Salicornia sp. (Fig. 7)
Screw press separation efficiency 100 %
Drum drying efficiency 100 %

Soxhlet extractions (Figs. 8 & 9)

Solvent evaporation 99 w%
Fig. 3. Schematic of distillation from Apsen HYSYS. Make-up solvent (of extractor volume) 1 w% h−1
Hexane extractor retention time 2 h
Hexane mixing 9.825 gℎ𝑒𝑥 g−1
𝑏𝑖𝑜𝑚𝑎𝑠𝑠
Hexane extractives 66.4 g𝑒𝑥𝑡. kg−1
𝑏𝑖𝑜𝑚𝑎𝑠𝑠
2.8. Techno-economic assessment EtOH extractor retention time 6 h
EtOH mixing 11.835 gEtOH g−1𝑏𝑖𝑜𝑚𝑎𝑠𝑠
EtOH extractives 35.5 g𝑒𝑥𝑡. kg−1
𝑏𝑖𝑜𝑚𝑎𝑠𝑠
A techno-economic assessment (TEA) is a crucial step when plan- Decanter liquid separation efficiency 99 w%
ning the construction of a processing plant or inputting new process
units and material streams to existing process plants. To analyze the
costs and revenues correlated to the production of sustainable jet fuel,
the SPD tool allows the user to examine the Economic Evaluation Generic boxes were used in the simulation with meta-data attached if a
Report (EER) showing detailed information about costs and revenues generic box was imitating a processing unit. Generic boxes can be used
from each production stream. Capital expenditure (CAPEX) and opera- for simplifications for the SPD user, as it allows for lower computational
tional expenditure (OPEX) are functions of the process plant size, and time and more flexibility. This unit procedure allows the user to make
corresponding building costs, staff salaries, material and chemical costs, a pseudo-reaction that does not affect the techno-economic assessment,
and utility used for heating and cooling. nor the energy and mass balances. This allowed the formation of non-
Labor rates were assigned for all processing units and for simplifica- existing intermediate products. An example of this generic box unit is in
tion, all equipment types have the same type of labor assigned. In SPD, Fig. 14, to split the BSFL lipids into its triglyceride profile, as specified
in Table 6.
the labor cost (LC) was determined from the basic salary, x, and the
Figs. 7 to 15 show the process built in detail, and with the simu-
model was run using the mean salary of operators in Denmark being
lation parameters defined in Tables 4 to 8 lies the foundation for the
20.6 USD h−1 [44]. On top of that, SPD took other labor-related costs
process simulation. All heating and cooling units were placed separately
in the form of coefficients and required labor hours, h, into account.
from reactors, evaporators, distillation towers, etc. as this allowed for
𝐿𝐶 = 𝑥𝑖 ⋅ (1 + 𝑎 + 𝑏 + 𝑜 + 𝑠) ⋅ ℎ (3) inter-stream energy recovery heat exchangers by the built-in process
option of energy recovery in SPD, and thereby saving utility expenses.
where a is administrative costs (0.6), b is benefits (0.4), o is operating Table 4 shows the operation and simulation parameters for the
supplies (0.1) and s is supervision (0.2), which were default coefficients Salicornia sp. preprocessing, and extractions. The first unit on Table 4,
from SPD. component splitting, is a redundant unit, as the purpose of this unit
Energy required for heating and cooling of streams under 140 ◦ C is to increase flexibility when changing one input stream, so the rest
was provided by utility such as steam at 152 ◦ C and cooling water at of the streams will scale accordingly. The streams leaving this com-
25–30 ◦ C, with a heat transfer coefficient of 1500 W m−2 ◦ C−1 and ponent splitting unit are inputs for pretreatment, enzymatic hydrolysis,
efficiency of 100%. All tanks and fermentors with the capability of feedstock production and HEFA-SPK processing. Input and output mass
stirring had stirring at 200 W m−3 . Most pumps in the simulated process flow rates are determined by laboratory-scale experiments. Shedding as
were inputted to overcome pipe pressure losses, with the pressure a process unit is implemented with the default SPD values.
difference being between 1 bar and 0.1 bar. Table 5 shows the operational parameters for hydrothermal pre-
treatment, enzymatic hydrolysis, feedstock mixing, stream splitting of
2.9. Simulation parameters in situ production of LPB. The stream was split before the in situ
production unit of LPB was to ensure the right cultivation conditions
For easy manipulation of input flows for sensitivity analysis, all of LPB. Values regarding hydrothermal pretreatment and enzymatic
input streams were controlled from one master input. This master input hydrolysis are based on the work done by Alassali et al. [24].
stream was split into its respective components of Salicornia sp., water Table 6 shows the blended hydrolyzed Salicornia sp. and CF feed-
for pretreatment, cellulase, CF, and hydrogen. All figures showing SPD stock operational conditions, feedstock fermentation conditions, BSFL
schematics have a red dot for the main input and a blue dot for the main cultivation conditions, BSFL processing conditions and the BSFL lipid
output, see Figs. 7–15. To ease building the process, the user can utilize profile. Lipid profiles of terrestrial animals are determined by the
the unit procedure Continuous 1 × 1 reaction generic box, see Fig. 12. provided feedstock, thus the lipid profile used in this study, described

6
M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

Table 5 Table 7
Operation and simulation parameters 2. All parameters determined by literature and Operation and simulation parameters 4.All parameters determined by literature study
laboratory work [24–30]. and SPD simulation [6].
Parameter Value Unit Parameter Value Unit
Pretreatment and enzymatic hydrolysis (Fig. 10) Hydrodeoxygenation and HI (Fig. 14)
Dry matter (DM) of slurry 6 w% H2 flow separation 50/50 w%
◦
before pretreatment HDO input temperature 310 C
◦ HDO thermal mode Adiabatic –
Pretreatment temperature 140 C
Pretreatment time 76 min HDO pressure 40 bar
◦ HDO lipid:H2 ratio 97.13/2.87 w%
Hydrolysis temperature 30 C
Hydrolysis time 24 h HDO retention time 1 h
◦
CF:Salicornia sp. ratio 60/40 w% HDO exit temperature 100 C
◦
Feedstock DM 14.1 w% Flash 1 temperature 50 C
before sludge drying Flash 1 pressure 1 bar
Feedstock DM 30.0 w% Decanter water separation 100 w%
HI input temperature 250 ◦
after sludge drying C
HI thermal mode Adiabatic –
Lactiplantibacillus plantarum cultivation (Fig. 11)
HI pressure 30 bar
Component splitting 92.07/7.93 w%
HI n-alkane:H2 ratio 96.50/3.50 w%
(excess juice:LPB culture ratio)
HI retention time 1 h
Salicornia sp. storage time 24 h ◦
◦C
HI exit temperature 227 C
LPB cultivation temperature 30
LPB fermentation time 24 h Fuel distillation (Fig. 15)
◦
LPB storage time 24 h Flash 2 temperature 35 C
Flow splitting 96.15/3.85 w% Flash 2 pressure 1 bar
◦
(storage:LPB culture ratio) 1st distillation tower temperature 190 C
2nd distillation tower temperature 218.5 ◦C

Table 6
Operation and simulation parameters 3. All parameters determined by literature and Table 8
laboratory work [31]. Input data for material and chemical costs.
Parameter Value Unit Parameter Value Ref.
[USD kg−1 ]
Feed fermentation and BSFL cultivation (Fig. 12)
◦ Buying prices
Storage temperature 30 C
Flow mixing 96.15/3.85 w% Salicornia sp. 0a –
(feedstock:LPB culture ratio) Hydrogen 2.00 [6]
Feedstock fermentation time 24 h Reaction water 0.0025 [45]
Feedstock storage time 24 h Cellulase 0.50 [46]
BSFL cultivation time 14 d CF 0.55 [23]
Parallel BSFL cultivation units 14 – EtOH 8.56 [47]
BSFL culture recycle 1 w% N-hexane 12.75 [47]
Steam (152 ◦ C) 0.012 SPD
BSFL processing (Fig. 13)
◦
Process cooling water (25–30 ◦ C) 0.00005 SPD
Devitalization temperature 140 C
Electricity 0.1b SPD
Screw press liquid separation 99 w%
Decanter lipid separation eff. 100 w% Selling prices
Decanter water separation eff. 70 w% Salicornia sp. lipids 1.00a –
Drum drying efficiency 100 % Salicornia sp. EtOH extract 7.00 [48]
Frass 2.00 [49]
BSFL lipid profile, generic box (Fig. 14)
BSFL screw-pressed cake 0.72 [23]
Tri-C12:0 39.4 w%
BSFL protein 2.17 [23]
Tri-C14:0 7.6 w%
BSFL lipids 0.30a –
Tri-C16:0 18.6 w%
Hydrogen 2.00 [6]
Tri-C18:0 5.0 w%
Propane 0.80 [6]
Tri-C18:1 23.6 w%
Naphta range fuel 0.55 [6]
Tri-C18:2 5.8 w%
HEFA-SPK range fuel 0.62 [6]
HVO range fuel 1.00 [6]

a Assumption.

by Li et al. [31], might deviate from the actual lipid profile of a BSFL b
USD kWh−1 .
culture partially fed with hydrolyzed Salicornia sp. Lipid profile of BSFL
from Li et al. was obtained from chicken manure fed BSFL [31].
Table 7 shows a summary of the HEFA process route conditions. As of the bacterial culture self-sustainable due to in situ production. The
the exit temperature of the HDO is 100 ◦ C, and some of the products price of the raw input biomass, Salicornia sp., is thought to be free, as
of the HDO reaction is water, some water will be in vapor phase and the biomass is a waste product after food production, and producers are
some in liquid phase. The flash evaporation column is cooled to 50 ◦ C in considering it as a waste product [48]. The cost of cellulase is based on
order to get a clear separation between the volatile non-polar n-alkanes an optimization research from by Kadhum et al. [46].
and the polar water. As the flow separation of hydrogen is set to 50/50 Table 9 shows the stoichiometric reactions included in the biorefin-
w%, the relative amount of hydrogen in the HI reactor compared to the ery model simulation.
HDO reactor, is higher. As a low amount of propane, but high amount of
longer alkanes, is desirable in the fuel, the propane rich product from
the HI reaction is flashed off at a relatively low temperature, 35 ◦ C, 2.10. Biorefinery section optimization
before fuel distillation.
Table 8 shows the buying and selling prices of chemicals, bulk mate- In order to successfully determine the possible gains or losses affil-
rials and utilities. Initial costs of LPB is not included, as the production iated by each processing section, Figs. 7–15, were tested in different

7
M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

Table 9 Table 12
All possible reactions with their respective stoichiometric coefficients. Mass balance of simulated HDO reactions.
Reaction Stoichiometry Type Compound In [w%] Out [w%]
Hydrodeoxygenation reactor H2 2.87 0.40
1 3 m ⋅ H2 + 1 tri−C18∶m → 1 tri−C18∶0 Molar H2 O – 8.73
2,3,5 6 H2 + tri−Cn∶0 → 3 CO Molar CO – 0.42
+ 3 C(n−1) H2(n−1)+2 + C3 H8 + 3 H2 O CO2 – 6.21
2,3,6,7 12 H2 + tri−Cn∶0 → 3 Cn H2n+2 Molar C3 – 5.74
+ C3 H8 + 6 H2 O C11 – 11.21
2,4 3 H2 + tri−Cn∶0 → 3 CO2 Molar C12 – 18.39
+ 3 C(n−1) H2(n−1)+2 + C3 H8 Tri-C12:0 38.27 –
C13 – 2.25
HI reactor
C14 – 3.65
8 H2 + Cn H2n+2 → Cn−3 H2(n−3)+2 + C3 H8 Molar
Tri-C14:0 7.38 –
9 H2 + Cn H2n+2 → Cn−8 H2(n−8)+2 + C8 H18 Molar
C15 – 5.69
10 H2 + Cn H2n+2 → Cn−7 H2(n−7)+2 + C7 H16 Molar
C16 – 9.14
11 H2 + C18 H38 → 2 C9 H20 Molar
Tri-C16:0 18.07 –
11 H2 + C16 H34 → 2 C8 H18 Molar
C17 – 10.86
12 Cn H2n+2 → i−Cn H2n+2 Molar
C18 – 17.32
Generic boxes Tri-C18:0 4.86 –
13 100 fermented feed → 0.93 NH3 Mass Tri-C18:1 22.92 –
+ 11.83 BSFL + 8.00 residue Tri-C18:2 5.63 –
+ 4.56 frass + 74.68 H2 O
14 100 BSFL → 22.54 BSFL lipid Mass
+ 32.00 protein + 45.46 residue
15 100 BSFL lipid → 39.4 tri−C12∶0 Mass and a small amount of CO. An issue with co-producing oxocarbons
+ 7.6 tri−C14∶0 + 18.6 tri−C16∶0
is the impact of GHG emissions, as the production of biofuels should
+ 5.0 tri−C18∶0 + 23.6 tri−C18∶1
+ 5.8 tri−C18∶2 aim to reduce the overall emission of CO2 -equivalents. Another issue
with the co-production of oxocarbons is the chemical energy in the
carbon-bonds should preferably be used in combustion, rather than as
Table 10 an emitted co-product. Another gaseous co-product is propane. Most of
Simulated process sections to determine the benefit of extra processing. Numbers in the propane is flashed off with CO2 and unreacted H2 , CO, H2 O and
the table refer to Figs. 7–15. some of the heavy alkanes. The reason for the partial removal of heavy
Process description Figures alkanes is due to the azeotropic properties of alkane mixtures. Of the
Salicornia sp. extract 7–9 flashed products after the HDO reactor, 0.26 w% is heavy alkanes. This
Salicornia sp. extract and BSFL products 7–13 amount can be decreased by lowering the flash temperature, thus also
Full simulation 7–15
shifting the propane/heavy alkane azeotrope to include more propane
in the fuel mixture.
Once reacted into n-alkanes, the stream is partially isomerized
Table 11
and hydrocracked into i-alkanes for fuel refinery. Table 13 shows the
Characterization of Salicornia sp. pulp and BSFL used for simulation. n/a: not
available.
input and output mass balance. Due to a higher amount of lighter
Compound Salicornia sp. pulp [w%] BSFL [w%]
alkanes formed (C7–C10), the share of these in the flashed products
will be higher, hence the temperature of the flash evaporation column
Water 86.39 61.45
Dry matter is lowered to 35 ◦ C (see Table 14).
Lipids 6.64 22.54 The heavy key distillation temperature of Jet A-1 is set to be 220 ◦ C,
EtOH solubles as it enables the separation of heavier hydrocarbons and yields the
- Ash 5.53 n/a jet fuel product matching the ASTM standards. Distillation at higher
- Others 3.32 n/a
Protein 10.92 32.00
temperatures results in the product including too many heavy alkanes,
Structural sugars increasing the freezing point above the standardized limit of −47 ◦ C.
- Arabinose 6.22 n/a Table 15 shows the distribution of alkanes in the final distilled fuels.
- Glucose 24.53 n/a
- Xylose 14.86 n/a
3.2. Techno-economic assessment results
Lignin 14.19 n/a
Exoskeleton n/a 9.00
Residue 13.79 36.46 Using techno-economic assessment (TEA) sensitivity analysis, a
range of input mass flow rates between 10–140 t h−1 has been chosen
for the simulation. Shpigel et al. [15] has reported the yearly harvest of
Salicornia sp. to be 26,000 kg fresh Salicornia sp. ha−1 . Of this amount,
scenarios, excluding specific processing sections. Table 10 shows dif-
8700 kg will be food grade biomass, and 17,300 kg will be residual
ferent inclusion scenarios to be simulated, and analyzed for feasibility.
biomass, corresponding to the biomass used for this simulation. SPD
3. Results has a default operational up-time of 330 days, 7920 h, per year, for a
process plant lifetime of 15 years. The biomass input mass flow rate of
This section describes the results reached from simulations done 10–140 t h−1 is thereby corresponding to the yearly harvest from 4580–
in SuperPro Designer and Aspen HYSYS. Water content and mass 64,090 ha, after the food grade biomass have been harvested. It should
components of Salicornia sp. and BSFL are shown in Table 11. be noted that this land could be salt affected, and would therefore
not compete with food production. Cultivation of 4580–64,090 ha
3.1. Simulation results Salicornia sp. might not be feasible for a small group of farmers, so
the biomass for a biorefinery of said size could be distributed over a
HDO, DCO2 and DCO reaction inputs and outputs are collected in nation. As an input mass flow rate above 80 t h−1 is relatively large,
Table 12, which show a large amount of H2 O and CO2 being produced the constraint of reactor and vessel volumes forces SPD to make parallel

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M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

Table 13 Table 15
Mass balance of simulated HI reactions. Comparison of distilled fuel products from BSFL lipid based HI alkanes in kg h−1 .
Compound Input [w%] Output [w%] Biorefinery input mass flow rate of Salicornia sp. of 10 ton h−1 .
Alkane Input Naphtha HEFA-SPK HVO
H2 3.50 3.13
C3 0.64 5.14 C3 0.3 0.3 0 0
C7 – 1.27 C7 2.1 1.7 0.4 0
C8 – 0.71 C8 1.4 1.0 0.4 0
i-C8 – 6.39 i-C8 14.3 10.0 4.0 0.3
C9 – 0.74 C9 1.6 0.8 0.7 0.1
i-C9 – 5.43 i-C9 11.8 6.8 4.4 0.6
C10 – 0.54 C10 1.2 0.5 0.6 0.1
i-C10 – 4.85 i-C10 10.8 4.9 4.9 1.0
C11 13.66 2.03 C11 4.5 1.4 2.3 0.8
i-C11 – 18.29 i-C11 40.9 13.9 20.6 6.4
C12 22.45 2.57 C12 5.8 1.2 3.0 1.6
i-C12 – 23.10 i-C12 51.8 12.7 26.6 12.5
C13 2.75 0.58 C13 1.3 0.2 0.6 0.5
i-C13 – 5.19 i-C13 11.7 2.0 5.7 4.0
C14 4.46 1.76 C14 4.0 0.4 1.5 2.1
i-C14 – 2.06 i-C14 4.6 0.5 2.0 2.1
C15 6.95 2.77 C15 6.2 0.4 1.9 3.9
i-C15 – 1.04 i-C15 2.3 0.2 0.8 1.3
C16 11.16 4.71 C16 10.6 0.4 2.6 7.6
i-C16 – 0.30 i-C16 0.7 0.1 0.2 0.4
C17 13.27 3.51 C17 7.9 0.2 1.4 6.3
i-C17 – 0.51 i-C17 1.1 0 0.3 0.8
C18 21.15 2.76 C18 6.2 0.1 0.8 5.3
i-C18 – 0.64 i-C18 1.4 0 0.3 1.1
𝛴 204.6 59.5 86.1 59.0

Table 14
Limits and common values for naphtha [43], HEFA-SPK [42] and HVO [43,50,51].
Parameter Naphtha HEFA-SPK HVO Unit
Limits/common values
Freezing point – <−47.0 <−10.0 ◦C

Density at 15 ◦ C – 775–840 780–890 kg m−3

Kinematic visc. – <8.0a 1.9–6.0b mm2 s−1
◦
Distillation temperature 70–180 >205–<300 240–340 C
Simulated products
Freezing point ◦
−64.9 −47.1 −18.8 C
Density at 15 ◦ C 772.8 786.4 789.1 kg m−3
Kinematic visc. 2.6a 4.2a 2.1b mm2 s−1
◦
Distillation temperature <190 190–220 >220 C
a
Kinematic viscosity at −20 ◦ C.
b
Kinematic viscosity at 40 ◦ C.

units. Due to parallel units being simulated, the capital expenditure

Fig. 4. Techno-economic assessment sensitivity analysis of the overall simulation.
(CAPEX) of the TEA is increased as the input mass flow rate exceeds a Parameters for techno-economic assessment includes return on investment, internal rate
limit just above 80 t h−1 . Considering the return on investment (ROI), of return and net present value.
this creates a local optimum at 80 t h−1 , as seen on Fig. 4. The revenue
streams from the biorefinery process includes Salicornia sp. revenue,
BSFL revenue and fuel revenue. Of these revenue streams, a direct (IRR) and net present value at 7% interest rate (NPV). The reason for
linear correlation to the input mass flow rate exists, meaning a 100% including multiple parameters in the TEA was due to the complexity
increase in input mass flow rate corresponds to a 100% increase in of a financial investment of such size. For an investment to be deemed
revenue. Expenses, CAPEX and operational expenditure (OPEX), are financially feasible, the ROI has to be larger than a certain threshold
independent and do not show linear correlation to the input mass set by the investor. In this case, the threshold was set to be >10 % yr−1 .
flow rate. This is as the price of the equipment follows a power law,
Furthermore, the NPV has to be positive over the process plant lifetime,
e.g. the increase in cost of centrifugal pumps per unit of electrical
as NPV is a measure of the total profit accounting for the interest rate,
power capacity, will decrease as the electrical power capacity increases.
set by SPD, of 7% in present value, over the process plant lifetime,
Table 16 summarizes the throughput, retention time, and simulation
which was set to be 15 years. IRR is a measure of the maximum interest
purchase price of equipment, apart from transport, mixing and utility
rate allowed for the process, allowing NPV = 0 after the process plant
equipment at a mass flow rate of 10 t h−1 . As the mass flow rate was
lifetime.
changed for sensitivity analysis, the throughput increased as a direct
linear correlation to the mass flow rate. All units did not increase 𝑁𝑒𝑡 𝑝𝑟𝑜𝑓 𝑖𝑡
𝑅𝑂𝐼 = (4)
retention time, apart from an exponential increase in decanter retention 𝐶𝐴𝑃 𝐸𝑋
time, which would exponentially increase the volume of said decanters ∑𝑡
𝑁𝑒𝑡 𝑝𝑟𝑜𝑓 𝑖𝑡𝑡
due to the fluid properties of the decanted liquids. The parameters 𝑁𝑃 𝑉 = − 𝐶𝐴𝑃 𝐸𝑋 (5)
𝑘=0
(107%)𝑡
for a TEA was found using internal calculations from SPD. The TEA
is dependent on multiple analysis parameters, and for this case, will Where t is the project lifetime in years, net profit𝑡 is the generated
include return on investment (ROI), internal rate of return after tax net profit in year t.

9
M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

Table 16
Process sizing and cost at 10 t h−1 . Transport, mixing and utility equipment
excluded.
Figure Equipment Throughput Retention time Purchase price
[kg h−1 ] [h] [1000 USD]
7 Screw press 10,000.0 1 274
7 Drum drier 1375.0 10 50
7 Shredder 1361.2 1 81
8 Extractor 14,735.1 2 44
8 Evaporator 14,735.1 1 23
8 Decanter 1495.0 0.006 34
8 Product storage 221.9 24 14
8 Solvent storage 13,373.9 24 267
9 Extractor 16,322.6 6 90
9 Evaporator 16,322.6 1 50
9 Decanter 1422.2 0.02 34
9 Product storage 270.4 24 13
9 Solvent storage 15,050.9 24 255
10 Pretreatment reactor 19,112.1 1.2 337 Fig. 5. Techno-economic assessment sensitivity analysis of simulation excluding biofuel
10 Storage 19,112.1 24 337 production. Parameters for techno-economic assessment includes return on investment,
10 Hydrolysis reactor 19,194.5 24 304 internal rate of return and net present value.
10 Sludge drier 20,919.5 1 33
11 Batch storage 392.5 24 71
11 Batch seed fermentor 408.2 24 945
11 Storage 392.5 24 52
12 Blending/Storage 9825.9 30 307
12 Fermentor 10,218.4 26.5 2833
12 Feedstock storage 10,218.4 30 157
12 BSFL cultivation unit 9825.9 336 124
12 Fly reproduction unit 12.1 168 6
13 Frass storage 7006.8 24 107
13 Devitalization unit 3104.5 1 353
13 BSFL storage 3104.5 24 73
13 Screw press 3104.5 1 108
13 BSFL residue storage 3104.5 24 73
13 Decanter 1 2555.0 0.05 34
13 Decanter 2 2289.5 1.02 56
13 Drum drier 955.9 1.7 152
14 HDO reactor 274.3 1 71
14 Flash 274.3 5.4 2
14 Decanter 239.1 0.004 34
14 HI reactor 224.6 1 71
15 Flash 224.6 31.5 1
Fig. 6. Techno-economic assessment sensitivity analysis of simulation excluding BSFL
15 Naphtha storage 59.5 24 4
refinery and biofuel production. Parameters for techno-economic assessment includes
15 HEFA storage 86.1 24 3
return on investment, internal rate of return and net present value.
15 HVO storage 59.0 24 4

increase in biofuel prices of 20% will yield a minor increase of the

Fig. 4 shows the techno-economic assessment parameters as the ROI from 17.55% to 17.79%, IRR from 11.35 to 11.60% and NPV
input mass flow rate of Salicornia sp. increases. ROI is above the set from 150,835,000 to 160,573,000 USD. This implies the majority of the
threshold of 10% at a input mass flow rate of >40 t h−1 , NPV is positive profits are not generated by the production of biofuels, as the product
at a input mass flow rate input of >60 t h−1 . NPV shows a large increase of highest revenue is the ethanolic extract.
at mass flow rates of >100 t h−1 . This increase is due to the larger
revenue relative to OPEX, compared to lower input mass flow rates. 3.4. Energy and carbon dioxide assessment
The TEA parameters shows to be stable, with little increase, at mass
flow rates of 60–100 t h−1 . This is due to the volume constraints from For the production of biofuels, the amount of energy released as
many of the operational units in SPD, as SPD will force the simulation heat by combustion of biofuels should exceed the amount of energy
of multiple parallel smaller units (see Table 17). used as electricity for the production of the biofuel. Likewise, the
amount of net-CO2 emitted by combustion of fossil fuels should be
3.3. Process optimization higher than the CO2 emitted by the production of sustainable biofuels.
The energy and net-CO2 balances for each of the subdivided production
The feasibility of the three simulation scenarios specified in Ta- steps was analyzed, and the potential energy released by stoichiometric
ble 10, were simulated individually, for a Salicornia sp. mass flow rate combustion of the produced naphtha, HEFA-SPK, HVO and flashed
of 10–140 t h−1 . These were simulated for comparison and with the propane was evaluated. Biofuel energy release was calculated using
objective of identifying the most feasible of the simulated processes. the lower heating value (LHV) of the fuel [52–55]. Furthermore,
The feasibility of the processes were interpreted from the financial to evaluate the CO2 -equivalent (CO2 -e) cost of production compared
analysis parameters. to reduced CO2 emission by biofuel combustion, the CO2 -e balance
Excluding processing of BSFL and jet-fuel shows to have a larger was calculated on a basis of production in Table 18, and on a basis
financial benefit, compared to inclusion of said processes, as seen from of product in Table 19. The CO2 reduction ratio, compared to CO2
Figs. 4–6. A positive NPV can be achieved at a lower input mass emitted by fossil fuels, was assessed. CO2 emitted by electricity power
flow rate of Salicornia sp. excluding processing of BSFL and biofuels. production in Denmark was in 2018 on average 306 g kWh−1 , and
Furthermore, with a Salicornia sp. mass flow rate of 140 t h−1 an CO2 emitted by stoichiometric combustion of gasoline, jet-fuel, diesel

10
M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

Fig. 7. 1: Preprocessing of Salicornia sp.

Table 17
Table of expense and revenue streams. In 1000 USD yr−1 .
Parameter Input mass flow rate [t h−1 ]
10 20 30 40 60 80 90 100 120 140
CAPEX 103,316 139,572 172,420 203,179 260,212 345,672 398,223 441,658 496,858 556,182
OPEX 45,232 62,097 80,227 97,968 132,199 172,563 193,671 227,152 248,522 282,693
Salicornia sp. revenue
Lipids 709 1418 2127 2836 4254 5672 6381 7090 8508 9926
EtOH extract 66,729 133,458 200,187 266,916 400,374 533,832 600,561 667,290 800,748 934,206
BSFL revenue
Frass 7381 14,762 22,143 29,524 44,286 59,048 66,429 73,810 88,572 103,334
Screw press residue 3177 6354 9531 12,708 19,062 25,416 28,593 31,770 38,124 44,478
Protein 6568 13,136 19,704 26,272 39,408 52,544 59,112 65,680 78,816 91,952
Fuel revenue
Flash 1 108 216 324 432 648 864 972 1080 1296 1512
Flash 2 183 366 549 732 1098 1464 1647 1830 2196 2562
Naphtha 259 518 777 1036 1554 2072 2331 2590 3108 3626
HEFA-SPK 423 846 1269 1692 2538 3384 3807 4230 5076 5922
HVO 467 934 1401 1868 2802 3736 4203 4670 5604 6538

Table 19
Table 18 Net-CO2 -e emitted per unit of product.
Energy and CO2 balance at a input mass flow rate of 10 ton h−1 .
Product Processes Net-CO2 -e emitted per
Process Power [kWh h−1 ] Net-CO2 -e emitted [kg h−1 ] product [kg CO2 -e kg−1 ]
Energy expense Salicornia sp. lipid 2 0.43
H2 production 409.6 125.3 Salicornia sp. EtOH extract 3 0.39
1 42.0 12.9 BSFL frass 4–7 0.03
2 125.7 38.5 BSFL screw press residue 4–7 0.02
3 153.0 46.8 BSFL protein 4–7 0.04
4 4.2 1.3 Flash 1 8–9 0.35
5 3.1 1.0 Flash 2 8–9 0.61
6 47.4 14.5 + 20.5a Naphtha 8–9 0.21
7 7.2 2.2 HEFA-SPK 8–9 0.14
8 107.5 32.9 + 18.7b HVO 8–9 0.21
9 30.7 9.4
𝛴 930.4 323.9
Produced fuels 2574.9 323.9
Equivalent fossil fuels 2574.9 659.5
respectively [58]. Most energy consumption of the process equipment
a
From the global warming potential of the biogenic emissions by BSFL assuming a was calculated by SPD as a function of mass flow rate and retention
feedstock carbon-to-nitrogen level of 25 [56].
b
time in the equipment. The energy usage for the process equipment that
From the global warming potential of the produced oxocarbons [57].
could not be calculated by SPD was calculated using a technical report
made by NREL [59]. As the HDO reactor emitted CO2 and CO directly
due to DCO2 and DCO, this is also included in the CO2 -e balance.
and propane, based on lower heating values, 259.3 g CO2 kWh−1 ,
257.5 g CO2 kWh−1 , 258.9 g CO2 kWh−1 and 240.2 g CO2 kWh−1 To be able to determine the real net-CO2 -e emitted by the process
respectively [58]. The produced biofuels are assumed to have similar and production of advanced biofuels, the emissions of co-products were
molecular composition as their respective fossil fuel counterparts, and calculated and normalized. Normalization of emissions expressed per
the combustion will therefore release the same amount of CO2 , with unit of product will allow a process designer to determine the actual
3.17, 3.11, and 3.07 kg CO2 per kg naphtha, HEFA-SPK and HVO emitted net-CO2 -e per mass unit of biofuel.

11
M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

Fig. 8. 2: N-hexane Soxhlet extraction. Input from Fig. 7.

Fig. 9. 3: Ethanol Soxhlet extraction. Input from Fig. 8.

Fig. 10. 4: Hydrothermal pretreatment and enzymatic hydrolysis of extractive free lignocellulosic Salicornia sp. Input from Fig. 9.

From Table 18 it can be seen the simulated production of biofuels lowered by utilizing excess power production by either photovoltaic or
and co-products from Salicornia sp. and Salicornia sp. fed BSFL emits wind energy. Combustion of these simulated produced biofuels yields
a net-amount of 323.9 kg CO2 h−1 , whereas the combustion of the an estimated net-CO2 -e reduction of 50.8%, with the co-production
similar fuel, excluding production and refining energy expenses, emits of terrestrial animal protein and EtOH extract with high bioactivity.
a net-amount of 659.5 kg CO2 h−1 . This carbon emission can be Furthermore, the produced biofuel holds 276.8% of the energy required

12
M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

Fig. 11. 5: Lactiplantibacillus plantarum cultivation in Salicornia sp. juice. Input from Fig. 7.

Fig. 12. 6: BSFL feedstock fermentation and BSFL cultivation. Input from Figs. 10 and 11.

Fig. 13. 7: BSFL processing. Input from Fig. 12.

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M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

Fig. 14. 8: BSFL lipid hydrodeoxygenation and HI. Input from Fig. 13.

Fig. 15. 9: Fuel distillation. Input from Fig. 14.

for the process itself. Regarding the normalized net-CO2 -e emitted, the from other 2nd generation biorefineries, as the characterized Salicornia
net-CO2 -e reduction of the naphtha, HEFA-SPK and HVO are 93.4%, sp. contains very low lignin content, and extensive pretreatment is
95.5% , 93.2% respectively. therefore not necessary prior to enzymatic hydrolysis. Furthermore, co-
products such as low-CO2 impact terrestrial animal protein and high
4. Discussion value bioactive extract are produced from the process. BSFL protein
are deemed low-impact CO2 -e protein, as the CO2 -e emitted per kg
Most implemented advanced bio-fuels such as HEFA-SPK or Fischer DM of BSFL can be 0.9–8.8% compared to traditional composting of
Tropsch-SPK use excess biomass from food crops, hence being 1st similar feedstock, dependent on the carbon-to-nitrogen level of the
generation bio-fuel. Some of this biomass comes from unsustainable feedstock which makes BSFL excellent low-CO2 -e impact food waste
sources as results of deforestation, extensive agricultural exploitation or bioconverters, with the frass having good fertilizing properties [56].
production of high yielding lipid or sugar crops for the sole purpose of Furthermore, the direct production of BSFL emits 0.14% CO2 -e per kg of
production of bio-fuels [60]. Cultivation of high-energy crops utilizes BSFL compared to the CO2 -e intensive production of cattle carcass [63].
arable land for production of energy. This poses a dilemma where
arable land and clean water are scarce resources, as cultivation of 5. Conclusions
crops for bio-fuels may reduce the food production [61]. Traditional
2nd generation bio-fuels are typically produced from waste biomass This paper has presented a full biorefinery process of Salicornia sp.
that can require energy-intensive pretreatments to be able to break the to jet-fuel. Salicornia sp. was fractionated into lipids, valuable ethanol
lignocellulosic structure, as the lignin content of these types of biomass extracted phytochemicals, and excess extractive-free biomass. The ex-
usually are relatively high, e.g. straw. Pretreatment of biomass will cess extractive-free biomass was then simulated to be hydrothermally
increase the amount of toxic furanic compounds and carboxylic acids, pretreated and enzymatically hydrolyzed, mixed with chicken feed, and
that could lead to poisoning of organisms used down-stream in the fermented with in situ produced Lactiplantibacillus plantarum. Hermetia
process [62]. The described process of Salicornia sp. biorefinery differs illucens, black soldier fly larvae, was added to the mixture of feedstock,

14
M. Fredsgaard et al. Biomass and Bioenergy 150 (2021) 106142

and devitalized after 14 days. Frass, protein and residual biomass [15] M. Shpigel, D. Ben-Ezra, L. Shauli, M. Sagi, Y. Ventura, T. Samocha, J.J. Lee,
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