LevulinicAcid Oct 2022

See discussions, stats, and author profiles for this publication at: https://www.researchgate.
net/publication/364383412
Levulinic Acid Production from Cellulosic Biomass – Process Modeling and

Techno-Economic Assessment (TEA) using SuperPro Designer.
Preprint · October 2022

DOI: 10.13140/RG.2.2.17520.53760
CITATIONS READS
0 920
3 authors:
Stoilas Stylianos Kontovas Nikiforos Misailidis

Aristotle University of Thessaloniki 45 PUBLICATIONS 254 CITATIONS
4 PUBLICATIONS 0 CITATIONS
SEE PROFILE
SEE PROFILE
Demetri Petrides
Intelligen, Inc.
153 PUBLICATIONS 1,143 CITATIONS
SEE PROFILE
All content following this page was uploaded by Demetri Petrides on 20 October 2022.
The user has requested enhancement of the downloaded file.

Levulinic Acid Production
Process Modeling and Evaluation using
SuperPro Designer®
by
Stylianos Kontovas, Nikiforos Misailidis and Demetri Petrides

October 2022
This is the ReadMe file of a SuperPro Designer example that analyzes the production of levulinic acid
from lignocellulosic biomass (corn stover in this case), based on a variation of the Biofine process that
has been commercialized by GF Biochemicals in Italy. Biomass hydrolysis and levulinic acid formation
take place in the same reactors. Formic acid, furfural and humins are co-produced in the process. The
products are separated and purified in the downstream section by a series of distillation columns
operating at different pressures and temperatures. The manufacturing plant analyzed in this example
processes 15 metric tons (MT) of corn stover per hour and generates 23,000 MT/year of levulinic acid,
11,000 MT/year of formic acid and 8,400 MT/year of furfural. The flowsheet of the process is appended to
the bottom of this document. You may test-drive this model by downloading the functional evaluation
edition of SuperPro Designer from the downloads page of our website (www.intelligen.com). All the files
of this example can be found in the Examples \ Bio-Materials \ LevulinicAcid folder. The default
installation path of the SuperPro Designer Examples folder follows below.
C:\ Users \ Public \ Public Documents \ Intelligen \ SuperPro Designer \ v# \ Process Library \ Examples
If you have any questions regarding this example or SuperPro Designer, please send an email message
to dpetrides@intelligen.com
INTELLIGEN, INC.
Simulation, Design, and Scheduling Tools
For the Process Manufacturing Industries
www.intelligen.com
Introduction
Over the last years, significant research has been focusing on developing efficient processes for the
conversion of biomass feedstocks into platform chemicals on a commercial scale, aiming to replace
petroleum-based fuels [1]. According to the United States Department of Energy [2], levulinic acid (LA)
could potentially be such a platform chemical since it is regarded as one of the top twelve value added
chemicals from biomass, forming a “chemical bridge” between biomass and petroleum processing [3].
LA is a linear C5-alkyl carbon chain that is known as 4-oxopentanoic acid or gamma ketovaleric acid and
3-acetylpropionic acid. It is a crystalline compound, and the commercial product is yellow to brown in color
with a caramellike odor. LA has a melting point of 33 ℃, boiling point of 246 ℃ and a density of around
1.1335 𝑔/𝑐𝑚3 while it is highly soluble in water, ethanol, ether, and acids [1]. It is characterized as a
moderately toxic substance and has a 𝑝𝐾𝑎 of 4.64 in water at 18 ℃ [4, 5]. Figure 1 shows the molecular
structure of levulinic acid, a short chain fatty acid whose molecular formula is 𝐶5 𝐻8 𝑂3 [6]. The LA molecule
consists of a ketone carbonyl group (𝐶 = 𝑂) and an acidic carboxyl group (𝐶𝑂𝑂𝐻). The combination of
these groups in the molecule make it highly reactive, enabling it to react with different functional groups to
form a wide range of derivatives. That is why LA is considered a platform chemical [1, 7].
Figure 1. The molecular structure of levulinic acid (2D) [6]
LA is produced from sugars. The first study on the synthesis of LA from sugars was reported in the 1840s
by the Dutch professor Mulder, who produced LA by heating sucrose with mineral acids (e.g., HCl and
H2SO4) as catalyst at high temperature [8]. Since then, there has been significant research studies on LA
production using sugars from various raw materials, including biomass. Different biomass precursors affect
the LA production yield considerably [9], so it is necessary to categorize them. According to Singoretto
et.al (2019) [6], the three different generations of biomass that can be used to produce LA are as follows:
i. First-generation biomass comes from food crops such as sugar, starchy crops, vegetable oil, or
animal fat.
ii. Second-generation of biomass is non-food crops, such as wood, organic waste, food crop waste,
and specific biomass crops. Lignocellulosic materials constitute the most common second-
generation biomass.
iii. Third-generation biomass comes from algae.
Intelligen, Inc. Page 2

The production of LA from the above feedstocks usually includes the following steps [6, 7, 10]:
i. Pretreatment of biomass (as needed for the specific feedstock)
ii. Hydrolysis of polysaccharides into monosaccharides
iii. Conversion of monosaccharides into LA
iv. LA purification
Biomass Pretreatment, Acid Hydrolysis and LA Production
This example focuses on LA production from second-generation biomass, so the pretreatment and
hydrolysis stages of the other two biomass feedstocks will not be discussed. The lignocellulosic biomass
pretreatment ensures that the feedstock is susceptible to complete hydrolysis of the polysaccharide fibers.
As such, the combination of the pretreatment and hydrolysis steps ultimately affect the LA production yield.
Numerous methods for the pretreatment and hydrolysis of the lignocellulosic biomass have been
developed, including alkali swelling, steam explosion, exposure to supercritical fluids etc. [11].
Lignocellulosic feedstocks, softwood, and hardwood, consist mainly of cellulose, hemicellulose, and lignin.
A combination of mechanical comminution, mild acid treatment at elevated temperatures to hydrolyze
hemicellulose, followed by enzymatic hydrolysis of cellulose, seems to provide a complete biomass
hydrolysis to sugars [12, 13]. The enzymatic hydrolysis of cellulose seems necessary, since cellulose does
not fully hydrolyze at the same temperature and pressure conditions, that the less tolerant hemicellulose
does.
However, the enzymatic hydrolysis of cellulose requires neutralization of the acidic slurry to adjust the pH
to values that will enable the enzyme to act. As it is later analyzed, the following step of the LA production
process, involves the conversion of sugars to LA. This reaction also requires acidic conditions and elevated
temperatures and pressures, which are in fact more severe than the hydrolysis conditions requirements.
Under these conditions, cellulose becomes susceptible to hydrolysis. As such, the neutralization and the
enzymatic hydrolysis of cellulose is not necessary to produce LA. The difference between the pretreatment
hydrolysis and the acid hydrolysis can be expressed via the combined severity factor (𝐶𝑆𝐹) [14]:
𝑇𝐻 − 𝑇𝑅
𝐶𝑆𝐹 = log [𝑡 ⋅ exp ( )] − 𝑝𝐻 (𝑬𝒒. 𝟏)
14.75
where t is the reaction time of the pretreatment in minutes, 𝑇𝐻 is the reaction temperature in ℃, 𝑇𝑅 is the
reference temperature, most often 100 ℃, and 𝑝𝐻 is the acidity of the aqueous solution in terms of acid
concentration. Literature suggests that 𝐶𝑆𝐹 for the pretreatment hydrolysis of corn stover should be 1 − 2,
while for LA production it should be larger than 3 [13, 15].

Figure 2. Simplified overview of LA production from lignocellulosic biomass. Source: [6, 13].
Figure 2 shows the reaction pathways of the three main components (A, B, C for cellulose, hemicellulose,
lignin, respectively) of lignocellulosic biomass. Route A shows that cellulose is hydrolyzed to glucose using
an acid catalyst. The generated glucose is then isomerized into fructose which undergoes dehydration
producing 5-hydroxymethylfurfural (HMF) as an intermediate [6]. HMF is finally rehydrated forming an
equimolar amount of LA together with formic acid (FA). Route B displays the reactions of hemicellulose
conversion. Hemicellulose is hydrolyzed easier than cellulose with acid catalyst, to form a mixture of its
constituents pentoses (e.g., xylose and arabinose) and hexoses (e.g., glucose, mannose, galactose)
monosaccharides [13]. The hexoses formed follow the reactions of Route A. Pentoses, which are the
predominant constituents of hemicellulose, follow the reactions of Route B. They are dehydrated to furfural,
which can be rehydrated to form furfuryl alcohol and then LA. It is also important to note that several side

reactions take place at various stages of the reactions sequence, which yield undesirable soluble and black
insoluble macromolecular materials, known as humins (Route D) [6, 16]. The presence of lignin facilitates
the formation of humins and results in a lower LA yield. Most of the lignin remains in solid state during
hydrolysis, and only a small portion of it dissolves in the reaction solution as acid soluble lignin (Route C)
[13].
Commercial Production of LA – the Biofine Process
The Biofine Process for the production of LA is the only process that has been industrially explored [17].
Figure 3 shows the stages and reactors required in the Biofine process, along with the chemical reactions
that take place in each of the reactors. A carbohydrate-containing lignocellulosic material is supplied
continuously to a plug flow reactor and hydrolyzed at 210-230 ⁰C for 13-25 seconds in the presence of
1% − 5% by weight mineral acid [18]. The hydrolysis releases sugars, which react to form HMF and water,
as shown in Figure 2. The slurry is then pumped to a continuous stirred tank reactor, which operates at
195-215 ⁰C with a residence time of 15-30 minutes, where HMF reacts to produce LA and formic acid.
Figure 3. Conversion of Cellulose to Levulinic Acid (main product), Formic Acid (byproduct) and Humins
(undesired byproduct) in the two Biofine reactors. Source: [19].
The CSF as calculated by 𝐸𝑞. 1 is about 2.2 in the plug flow reactor and around 4 in the back mix reactor.
These values agree with the CSF ranges for the hydrolysis and LA production, respectively.

In parallel with the main reaction scheme that produces LA, part of the hydrolyzed sugars react to generate
other intermediates, which tend to cross-react and coalesce to form an acid-resistant tar, which consists of
many insoluble residues such as humins. The theoretical yield of LA from hexoses is 64.4%, but the actual
yield achieved through the various processes is usually limited to 50-60% of the theoretical yield [13]. The
actual yield to LA depends on the reactor layout and operating conditions, which might favor LA production
or humins formation [19].
The Biofine Process has reduced char formation and achieves LA from cellulose yields of 70 − 80% of the
theoretical maximum [19]. This corresponds to a conversion of approximately 50% of the mass of 6-carbon
sugars to LA, with 20% being stoichiometrically converted to formic acid, and the remaining 30% being
converted to humins. The mass yield of furfural from 5-carbon sugars is also approximately 70% of the
theoretical value of 72.7%, equivalent to 50% of the mass, the remainder being treated as humins.
Levulinic Acid Purification – Downstream Processing
As mentioned above, hydrolysis of lignocellulosic biomass and reaction for LA production leads to a
complex slurry which requires purification. The aqueous mixture consists of 3 − 8%(𝑤𝑡) LA, 1 − 5% formic
acid and 1 − 5% furfural [20]. Formic acid and furfural form azeotropes with water making the purification
process highly energy demanding [21]. For this reason, hybrid schemes have been proposed for the
purification of LA to remove excess water using liquid-liquid extraction, reactive extraction and other
concepts that reduce energy consumption (e.g., dividing wall columns) [20, 22, 23]. In this example, LA,
formic acid, and furfural is purified through a series of consecutive distillations [22]. The purity targets were
set at 98%, 85% and 99% for LA, formic acid, and furfural, respectively [22].
Various companies have pursued the commercial production of LA from lignocellulosic feedstocks, but the
Italy-based biochemical manufacturing firm GF Biochemicals is regarded as the pioneer of commercial
production of LA [17]. It started commercial production in 2015, making its commercial scale LA plant the
world’s largest, and it scaled up to full capacity of 10,000 𝑀𝑇/𝑦 in 2017 [24].
Presently, levulinic acid finds applications in pharmaceuticals, pesticides, cosmetics, food additives, and
minor uses in nylons, synthetic rubbers, and plastics. The global LA market size stood at $27.2 million in
2019 and $28.3 million in 2021 [17]. It is anticipated that the global LA market will increase with an annual
growth rate of more than 8% during the period of 2021-2030 [25, 26]. However, the true potential of the
molecule is much higher than the current market size. Figure 4 summarizes some of the LA derivatives.
These include levulinate esters, 𝛾-valerolactone (GVL), acrylic acid, 1,4-pentadiol, angelica lactone, 2-
methyltetrahydrofuran (MTHF), 𝛿-aminolevulinic acid (DALA), tetrahydrofuran (THF) and many others [9].
The LA derivatives can be used as fuel additives, solvents, resins, chemical intermediates, polymers,
electronic materials, batteries, adsorbents, photography, plasticizers, rubber, cosmetics, drug delivery
systems, textiles, and pharmaceutical products [6]. Table 1 shows the LA amounts that would be needed,

if some chemicals were produced using LA as feedstock. Clearly, some derivatives have the potential to
increase the current LA global market size manyfold. The current LA selling price ranges between $5-$8/kg.
For LA to become a major platform chemical, its selling price needs to be reduced to around $1/kg. Ongoing
R&D projects focus on reducing the production costs, and it is expected that LA produced from sustainable
feedstocks will become much more competitive in the coming years.
Figure 4. Potential LA derivatives and applications. Source: [13].
Table 1. Potential LA markets demand for some possible products from LA [8]
Product Use Potential LA market (million kg/ year)
MTHF Fuel extender 4,500 − 45,000
DALA Biodegradable herbicide 60 − 120
Diphenolic Acid Monomer 16
THF Solvent 90

Process Description
A conceptual process for LA production was modeled and economically evaluated using SuperPro
Designer to estimate the expected material requirements, process equipment, utilities consumption and
ultimately production costs. For reporting and analysis purposes, the process has been divided into four
sections:
➢ Pretreatment and Reaction to LA (black icons)

➢ Levulinic Acid Separation (violet icons)
➢ Formic Acid Separation (blue icons)
➢ Furfural Separation (orange icons)
Flowsheet sections in SuperPro are simply sets of related unit procedures (processing steps). For
information on how to specify flowsheet sections and edit their properties, please consult the Help Facility
of the tool and/or Chapter 8.1 of the manual. The contents of each process section are described in
greater detail next. The flowsheet of the process is appended to the bottom of this document.
Pretreatment and Reaction to LA

The purpose of this process section is to convert corn stover to LA. Table 2 shows the assumed
composition of corn stover. Corn stover is treated as a Stock Mixture in SuperPro Designer since it is a
mixture of pure components. Information on Stock Mixture specification can be found in Chapter 15.6 of
the SuperPro manual.
Table 2. Chemical composition of corn stover

Component w/w %
Cellulose 30
Hemicellulose 22
Lignin 16
Ash 4.7
Proteins 2.8
Solubles 4.5
Water 20
The incoming corn stover enters the process through a storage bin (P-0 / SB-101). It is then conveyed
through a belt conveyor (P-1 / BC-101) to a grinder (P-2 / GR-101) where it is ground. The final particle size
needs to be between 0.5 and 1 𝑐𝑚 to ensure efficient hydrolysis and optimum yields [19]. The ground corn
stover is mixed with a recycled water stream (which will be later analyzed) in a custom mixer (P-3 / MX-
101) to reach a final water content of 70%. The slurry is then mixed with 92% 𝑤/𝑤 sulfuric acid using
another custom mixer (P-5 / MX-102) to a final sulfuric acid concentration of 3% 𝑤/𝑤. The slurry is then
pumped (P-6 / PM-102) to a final pressure of 26 bar and preheated in a heat exchanger (P-7 / HX-101)
against a hot stream which will be later analyzed. High pressure steam is used to increase the slurry

temperature to around 215 ℃ in a heater (P-8 / HX-102). The slurry enters a plug flow reactor (P-9 / PFR-
101) that operates with an average residence time of 12 seconds where cellulose and hemicellulose are
hydrolyzed and generate 5-hydroxymethylfurfural (HMF), furfural and LA according to the following reaction
stoichiometries and conversions.
Reactions taking place in the PFR Conversion
Hemicellulose Hydrolysis (Mass Stoichiometry)

162 Hemicellulose + 18 Water → 2 Acetic Acid + 27 Hexoses + 151 Pentoses 99%
Cellulose Hydrolysis (Mass Stoichiometry)
162 Cellulose + 18 Water → 180 Hexoses 75%
Hexoses to HMF (Molar Stoichiometry)

1 Hexoses → 1 HMF + 3 Water 95%
Pentoses to Furfural (Molar Stoichiometry)

1 Pentoses → 1 Furfural + 3 Water 95%
HMF to Levulinic Acid (Molar Stoichiometry)

1 HMF + 2 Water → 1 Levulinic Acid + 1 Formic Acid 10%
As shown above, hemicellulose is nearly fully converted during this stage, since it is more easily hydrolyzed
than cellulose. It is also assumed that most of the hexoses deriving from the cellulose hydrolysis are
converted into HMF, which is subsequently transformed to a small extent into LA.
The slurry is then adiabatically flashed in a flash tank (P-10 / V-101) to a final pressure of around 14 𝑏𝑎𝑟𝑠,
corresponding to a temperature of about 195 ℃. The vapors formed are condensed (P-11 / HX-103) against
cooling water and the condensate used later in the process. The liquid slurry from the P-10 flash tank enters
a continuous stirred tank reactor (P-12 / R-101) which operates with a residence time of 20 𝑚𝑖𝑛, while the
temperature and pressure are controlled at 195 ℃ and 14 𝑏𝑎𝑟, respectively. The table below lists the
reactions taking place in the CSTR.
Reactions taking place in the CSTR Conversion
Cellulose Hydrolysis (Mass Stoichiometry)

162 Cellulose + 18 Water → 180 Hexoses 75%
Hemicellulose Hydrolysis (Mass Stoichiometry)

162 Hemicellulose + 18 Water → 2 Acetic Acid + 27 Hexoses + 151 Pentoses 99%
Furfural Formation (Molar Stoichiometry)

1 Pentoses → 1 Furfural + 3 Water 100%

5-Hydroxymethylfurfural (HMF) Formation (Molar Stoichiometry)
1 Hexoses → 1 HMF + 3 Water 100%
Levulinic Acid Formation (Molar Stoichiometry)

1 HMF + 2 Water → 1 Levulinic Acid + 1 Formic Acid 85%
Humins Formation (Mass Stoichiometry)
100 HMF → 70 Humins + 30 Water Soluble Humins 100%
Formic Acid Formation (Mass Stoichiometry)

100 Furfural → 30 Formic Acid + 35 Humins + 35 Water Soluble Humins 50%
Ultimately the resulting slurry contains around 7.2 %(𝑤𝑡) LA, 3.5 % FA and 2.3 % furfural. This hot stream
is cooled down in the feedstock preheater (P-7 / HX-101) against the incoming cold slurry.
Levulinic Acid Separation
The slurry is then pressed in a screw press (P-13 / SP-101), separating the solids from the liquid. The cake
is washed with water and filtered in two belt filter presses connected in series (P-14 / BF-101, P-15 / BF-
102) and finally is disposed of as solid waste. The filtrates of the filtration units are combined using a 2-
stream mixer (P-17 / MX-103) and stored in a buffer tank (P-18 / V-103).
The mixture is then heated to 80 ℃ (P-19 / HX-105) and sent to a distillation column (P-20 / C-101), which
removes the more volatiles (water, formic acid, and furfural) in the distillate. The stillage is sent in another
distillation column (P-22 / C-102), which separates the LA in the distillate from the remaining components.
The distillate is cooled down to 35 ℃ against cooling water (P-24 / HX-106) and delivered at commercial
purity (> 99%). The stillage of the P-22 column is sent to wastewater treatment.
Formic Acid Separation
The distillate stream of the first distillation column (stream S-137) is an aqueous mixture of a considerable
quantity of FA and furfural. These are purified and sold as byproducts. For that purpose, the distillate (S-
137) is sent to a buffer tank (P-26 / V-104), in which it is mixed with a recycling stream that will be later
discussed, and then fed to a distillation column (P-28 / C-103), which operates at a pressure of 2 bar and
removes more than 98% of the content water in the distillate stream. The bottom stream (S-141) which
mainly consists of FA and water (75.1% and 22.4% respectively) is fed to another distillation column (P-29
/ C-104), which operates at a lower pressure of 0.27 bar. The distillate of P-29 containing the recovered
formic acid (FA) is cooled down against cooling water (P-31 / HX-107) and delivered with an FA composition
of > 85% in compliance with the commercial purity target. The stillage of the low-pressure column P-29
(stream S-139) is recycled and mixed with the feed stream (S-137) in the supply buffer tank (P-26 / V-104).
Furfural Separation

The distillate of the formic acid separation high-pressure column (stream S-146), which contains 2.6% 𝑤𝑡
furfural and 97.3% water is sent to the furfural separation section. This stream is initially mixed with the
condensate of the condenser P-11 and other 2 recycle streams (which will be discussed later) in a 4-stream
mixer (P-33 / MX-105). The resulting mixture is sent to a distillation column (P-34 / C-105), which separates
the furfural in the distillate, while most of the water exits the column in the stillage. Water and furfural are
not fully miscible. The distillate of the column P-34 is delivered at a concentration of furfural above its
solubility. As such, the distillate of the distillation column P-34 is cooled down in a cooler (P-35), to reduce
the furfural-water mixture solubility to about 80 𝑔/𝐿, and then passed through a decanter, which separates
the light water phase from the heavier furfural phase [27, 28]. The light water phase, containing a
considerable amount of dissolved furfural, is sent back to the first distillation column P-34 via the P-33
mixer. The organic phase with a composition of around 92.3% 𝑤𝑡 furfural, is preheated in a heat exchanger
(P-37 / HX-112) and fed to another distillation column (P-38 / C-106) where furfural is recovered in the
stillage. The stillage is sent to the preheater (P-37 / HX-112) to exchange heat with the feed stream, which
requires heating, and then cooled down in a cooler (P-41 / HX-110) against cooling water.
Finally, the stillage of the first furfural separation column (P-34 / C-105), which is almost pure water is cooled
down in a cooler (P-42 / HX-111) and recycled back to the beginning of the process via a custom flow
splitter (P-44 / FSP-101).
Virtual Heat Recovery
This process includes multiple virtual heat recovery matches. Table 1 displays detailed information on the
selected heat recovery matches. The condenser of the C-102 column condenses vapors at 161.1 ⁰C,
whereas the reboiler of the C-101 column operates at 145.9 ⁰C. This offers an opportunity for heat recovery,
in which a small fraction (2.51%) of the steam requirement of column C-101, is saved using the condensing
vapors of the C-102. The hot stream is matched at 100%, meaning no cooling water is needed. Similarly,
the condenser of the C-103 column condenses vapors at 119.6 ⁰C, whereas the reboiler of the C-104
column operates at 71.7 ⁰C, and the C-101 column heater (HX-105) needs to heat up the column feed to
80 ⁰C. All the steam requirements of column C-104 and the preheater HX-105 are satisfied using 5.97% of
the flow of the condensing vapors of C-103. Earlier in the process the HX-103 condenser can partially
supply the heat requirements of the heater HX-102. Similarly, the heat of the HX-108 cooler can partially
supply the heat requirements of the reboiler of column C-105. Detailed information on how to identify and
specify virtual heat recovery matches can be found in the ReadMe files of the Biodiesel and the Corn
Refinery examples of SuperPro.

Table 3. Heat recovery matches in the process
Heat recovery Hot Tin Hot Tout Cold Tin Cold Tout Hot Cold
Hot / Cold Match % Match %
C-102/ C-101 161.1 161.1 145.9 145.9 100.0 2.51
C-103/ C-104 119.6 119.6 71.7 71.7 2.57 100
C-103/ HX-105 119.6 119.6 51.9 80.0 3.4 100
HX-103/ HX-102 195.2 180.0 185.6 215.0 69.38 31.16
HX-108/ C-105 119.6 99.0 100.0 100.0 70.76 10.31
Economic Evaluation
This plant produces 23,000 MT of levulinic acid (LA) per year. In addition, it co-produces around 13,000
MT of formic acid (85%) and 8,400 MT of furfural per year. Various assumptions were made for the costs
of raw materials, heat transfer agents, wastewater treatment, equipment purchase costs, labor etc. In
addition to the mass and energy balances, SuperPro Designer calculates the capital (CAPEX) and
operating expenses (OPEX), the production cost and the profitability of the project. The results can be found
in the Economic Evaluation (EER), Cash Flows Analysis (CRF), Itemized Cost (ICR) and Excel Custom
reports. Table 4, which was extracted from the ERR and is shown below, provides information on
equipment sizes and purchase costs. The SuperPro Designer built-in cost models were used for estimating
the purchase cost of most equipment. User-defined cost-models were used for few. The specification of
User-defined cost models is explained in detail in the manual and in the ReadMe file of the Corn Refinery
example of SuperPro. Table 5, which was also extracted from the ERR, provides an estimate of the Direct
Fixed Capital Cost, which is around $97.8 million for a plant of this capacity.
4. EQUIPMENT SPECIFICATION AND FOB COST (2022 prices)
Main Equipment
Quantity/ Unit Cost
Standby/ Name Description Cost ($)
($)
Staggered
1/0/0 R-101 Stirred Reactor 2,000,000 2,000,000
Vessel Volume = 15,73 m3
1/0/0 SB-101 Solids Bin 1,543,000 1,543,000
1/0/0 C-103 Rigorous Distillation Column 1,300,000 1,300,000
Column Volume = 42,07 m3
1/0/0 BF-101 Belt Filter 1,125,000 1,125,000
Belt Width = 4,02 m
1/0/0 BF-102 Belt Filter 1,125,000 1,125,000
Belt Width = 4,02 m
1/0/0 PFR-101 Plug Flow Reactor 1,000,000 1,000,000
1/0/0 SP-101 Screw Press 920,000 920,000
Throughput = 40575,13 kg/h
1/0/0 C-101 Rigorous Distillation Column 913,000 913,000

1/0/0 HX-101 Heat Exchanger 758,000 758,000
Heat Exchange Area = 1714,80 m2
1/0/0 V-103 Blending Tank 577,000 577,000
1/0/0 V-104 Blending Tank 559,000 559,000
1/0/0 V-102 Decanter Tank 408,000 408,000
1/0/0 GR-101 Grinder 398,000 398,000
Rated Throughput = 15000,00 kg/h
1/0/0 BC-101 Belt Conveyor 302,000 302,000
Belt Length = 100,00 m
1/0/0 PM-102 Centrifugal Pump 100,000 100,000
Pump Power = 38,71 kW
1/0/0 HX-103 Condenser 38,000 38,000
Condensation Area = 3,98 m2
1/0/0 V-101 Flash Drum 22,000 22,000

Unlisted Equipment 3,644,000
TOTAL18,219,00018,219,000
5. FIXED CAPITAL ESTIMATE SUMMARY (2022 prices in $)
5A. Total Plant Direct Cost (TPDC) (physical cost)

1. Equipment Purchase Cost 18,219,000
2. Installation 6,160,000
3. Process Piping 6,377,000
4. Instrumentation 7,288,000
5. Insulation 547,000
6. Electrical 1,822,000
7. Buildings 2,733,000
8. Yard Improvement 2,733,000
9. Auxiliary Facilities 7,288,000
TPDC 53,166,000
5B. Total Plant Indirect Cost (TPIC)

10. Engineering 13,292,000
11. Construction 18,608,000
TPIC 31,900,000
5C. Total Plant Cost (TPC = TPDC+TPIC)

TPC 85,066,000
5D. Contractor's Fee & Contingency (CFC)

12. Contractor's Fee 4,253,000
13. Contingency 8,507,000
CFC = 12+13 12,760,000
5E. Direct Fixed Capital Cost (DFC = TPC+CFC)

DFC 97,826,000
Tables 6a,b,c provide information on the assumed unit costs and the calculated annual amounts and costs
of a) raw materials, b) labor and c) utilities. The total annual cost of raw materials is around $10.9 million.
According to Table 6b, the cost of labor is approximately $12.7 million per year. Table 6c displays the

utilities costs, which were estimated to be about $28.4 million per year. Note that the savings due to the
virtual heat recovery were estimated to be around $1.5 million per year.
6a. MATERIALS COST - PROCESS SUMMARY
Unit Cost Annual Annual Cost

Bulk Material %
($) Amount ($)
Corn Stover 80.00 118,800MT 9,504,000 87.32
Sulfuric Acid 0.12 9,892,473kg 1,187,097 10.91
Water 3.00 64,220MT 192,661 1.77
TOTAL 10,883,757 100.00
NOTE: Bulk material consumption amount includes material used as:

- Raw Material
- Cleaning Agent
- Heat Transfer Agent (if utilities are included in the operating cost)
6b. LABOR COST - PROCESS SUMMARY
Unit Cost Annual Amount Annual Cost

Labor Type %
($/h) (h) ($)
Operator 69.00 183,857 12,686,143 100.00
TOTAL 183,857 12,686,143 100.00
6c. UTILITIES COST (2022 prices) - PROCESS SUMMARY
Unit Cost Annual Ref. Annual Cost

Utility %
($) Amount Units ($)
Std Power 0.10 16,221,202 kW-h 1,622,120 5.72
Steam 24.00 887,513 MT 21,300,304 75.14
Steam (High P) 30.00 29,631 MT 888,936 3.14
Cooling Water 0.05 90,715,325 MT 4,535,766 16.00
TOTAL 28,347,156 100.00
Note: The utilities cost is reduced by 1511387 $/yr due to heat recovered in the process.
Figure 5 provides a breakdown of the total annual operating costs. Clearly utilities, facility-dependent
(depreciation of the capital investment, maintenance, etc.) and labor costs have the highest contribution to
the total annual operating costs, accounting for 38%, 25% and 17%, respectively. Finally, Table 7 displays
the executive summary. The total CAPEX required was estimated to be about $107.7 million. For a selling
price of $3/kg LA, the expected payback time is around 5.5 years.

Figure 5. Annual Operating Cost Breakdown (%)
7. EXECUTIVE SUMMARY (2022 prices)
Total Capital Investment 107,670,00 $

Capital Investment Charged to This Project 0$
107,670,00
Operating Cost 0 $/yr
74,946,000
Main Revenue 68,709,000 $/yr
Other Revenues 19,819,579 $/yr
Total Revenues 88,529,000 $/yr
Cost Basis Annual Rate 22,903,128 kg MP/yr
Unit Production Cost 3.27 $/kg MP
Unit Production Revenue 3.87 $/kg MP
Gross Margin 15.34 %
Return On Investment 18.09 %
Payback Time 5.53 years
IRR (After Taxes) 11.23 %
NPV (at 7,0% Interest) 30,314,000 $
MP = Total Flow of Stream 'Levulininc Acid'
Summary
The objective of this example is to present a levulinic production model in SuperPro Designer that is easy
to understand and follow. As indicated in the preceding analysis, a plant with a capacity of around 23,000
metric tons of levulinic acid per year requires a total CAPEX of around $108 million and annual operating
expenditures (including depreciation) of around $75 million. The predominant cost is the cost of utilities,
followed by the facility-dependent costs. The payback time of this investment was estimated to be arond
5.5 years.

Appendix – VLE Charts
The pressure dependency of the “formic acid – water” azeotrope can be observed in the relevant vapor-
liquid equilibrium (VLE) charts which can be generated by SuperPro Designer. In this example, the
Rigorous Physical State Calculation Toolbox was used for the procedures that perform VLE calculations,
such as Flash Evaporation and Distillation. The PS calculation toolbox can be defined at a flowsheet level
for the entire process, or at an individual procedure or at an individual operation or stream. In the present
example, the overall process utilizes the Shortcut Toolbox, while the Flash Evaporation and Distillation
procedures utilize the Rigorous Toolbox. The user can define the PS. Calc. Toolbox for the overall process
by right-clicking on an empty area of the flowsheet and selecting PS Calculation Options… ⇒ Shortcut
vs. Rigorous… or, alternatively, by selecting Edit ⇒ Process Options⇒ PS Calculation Options⇒
Shortcut vs. Rigorous… from the application’s main menu bar. This brings up the dialog shown in Figure
6, which allows the user to switch between the Shortcut and the Rigorous Toolbox.
Figure 6. Shortcut vs. Rigorous Physical State Calculation Toolbox Selection
In addition, by clicking on the corresponding View/Edit button, the user can specify the default options for
each PS toolbox. Figure 7 shows the Default Shortcut PS Calculation Toolbox options. In this window, the
physical state of each component can be specified according to one of the following criteria:
➢ Normal Boiling Point

➢ Liquid/Solid Only
➢ Vapor Only
➢ Vapor Pressure (Antoine)
The user can find details about each one of these categories in the Farnesene example or in the Help
facility.

Figure 7. Shortcut Physical State Calculation Toolbox Default Options
As mentioned earlier, although the Shortcut Toolbox was selected for the overall process in this example,
the Rigorous Toolbox was used for individual procedures, and therefore the default options for the Rigorous
Toolbox also had to be defined. This was done by clicking on the View/Edit button below the “Rigorous PS
toolbox” of Figure 6, prompting the Rigorous PS Toolbox dialog, shown in Figure 8.

Figure 8. Rigorous Physical State Calculation Toolbox Default Options
In the Rigorous Toolbox window, users can select the VLE model they wish to use, specify the binary
coefficients of components, and plot binary phase diagrams based on that model. Figure 8 shows the VLE
model used in the flash and distillation procedures, which in this model was Modified Raoult’s Law
parametrized with NRTL binary coefficients. Figures 9 and 10 show the NRTL a and NRTL g tabs, in which
the user can specify the binary coefficients of the relevant components.
Figure 9. NRTL a tab in the “Rigorous Physical State Calculation Toolbox Default Options” window

Figure 10. NRTL g tab in the “Rigorous Physical State Calculation Toolbox Default Options” window
The NRTL tabs work like spreadsheets, and values available in the database of SuperPro are automatically
filled in. The binary coefficients between Water, LA, FA and Furfural that were necessary in this example
were inserted manually using data from the literature [29].
After the VLE model and its parameters are defined, the user may click on the “Plot Binary VLE Chart”
button shown in Fig. 8, which brings up the Binary Chart window. Through this window, it is possible to
generate binary VLE diagrams for different component pairs. Figure 11 shows the VLE chart for the mixture
of FA and water. This chart was created by selecting FA as “Component A”, and Water as “Component B”
and then clicking on the “Plot…” button. The data obtained from SuperPro can be exported to MS Excel,
through the “Export Data to Excel” options. The charts of Figure 12 were generated in Excel using the
“Export Data to Excel” functionality.

Figure 11. Binary Chart window. V stands for vapor phase; L stands for liquid phase; and V+L stands for
a mixture of liquid and vapor.
Figure 12 shows that the “formic acid – water” azeotrope composition is shifted at different pressures. At a
pressure of 0.27 bar, 1 bar and 2 bar, the azeotrope contains approximately 43%, 54% and 58% mol of FA.
This is the basis of the design of the separation of formic acid and water in the current example. The design
involves two columns operating at different temperatures (pressure swing distillation) [30]. The increased
pressure in the first column (P-28 / C-103) causes an increase in the formic acid composition in the
azeotrope (~58% 𝑚𝑜𝑙 FA at 2 𝑏𝑎𝑟). Thus, the bottom product stream (S - 141) is delivered at a composition
of roughly 57.7% 𝑚𝑜𝑙 FA. The second distillation operates at a lower pressure, which lowers the formic
acid composition in the azeotrope (~43% 𝑚𝑜𝑙 FA at 0.27 𝑏𝑎𝑟). After this pressure change, the stream (S -
141) exists at a composition which is above the azeotrope, thus allowing further concentration of formic in
the rectifying section, achieving a final composition of about 69.8% 𝑚𝑜𝑙 FA (corresponding to roughly 86%
w/w).

74 110
P=0.27bar
P=1.01bar
72
108
70
Temperature (℃)
Temperature (℃)
106
68
66
104
64
102
62
x=0.43 x=0.54
60 100
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole Fraction of Formic Acid Mole Fraction of Formic Acid
132
P=2.00bar
130
Temperature (℃)
128
126
124
122
x=0.58
120
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole Fraction of Formic Acid
Figure 12. The azeotropic composition in the “formic acid – water” mixture due to pressure change (blue:
liquid composition / boiling point curve, red: vapor composition / dew point curve)

References
[1] Morone A, Apte M, Pandey RA. Levulinic acid production from renewable waste resources:
Bottlenecks, potential remedies, advancements and applications. Renewable and Sustainable
Energy Reviews 2015; 51: 548–565.
[2] Werpy T, Petersen G. Top Value Added Chemicals from Biomass Volume I - Results of Screening
for Potential Candidates from Sugars and Synthesis Gas. Washington, DC, USA, 2004.
[3] Bozell JJ. Connecting Biomass and Petroleum Processing with a Chemical Bridge. Science (1979)
2010; 329: 522–523.
[4] Lewis RJ. Sax’s Dangerous Properties of Industrial Materials Eleventh Edition, www.copyright.com.
(2004).
[5] National Library of Medicine. COMPOUND SUMMARY - Levulinic acid.

https://pubchem.ncbi.nlm.nih.gov/compound/Levulinic-acid.
[6] Signoretto M, Taghavi S, Ghedini E, et al. Catalytic Production of Levulinic Acid (LA) from Actual
Biomass. Molecules (Basel, Switzerland); 24. Epub ahead of print 30 July 2019. DOI:
10.3390/molecules24152760.
[7] Bahú J, Bonon A, Ingrid Rocha Barbosa M, et al. Levulinic Acid as a Chemical Platform to Polymers.
2021; 3: 7.
[8] Yan K, Jarvis C, Gu J, et al. Production and catalytic transformation of levulinic acid: A platform for
speciality chemicals and fuels. Renewable and Sustainable Energy Reviews 2015; 51: 986–997.
[9] Pileidis FD, Titirici M-M. Levulinic Acid Biorefineries: New Challenges for Efficient Utilization of
Biomass. ChemSusChem 2016; 9: 562–582.
[10] Jiang Z, Hu D, Zhao Z, et al. Mini-review on the synthesis of furfural and levulinic acid from
lignocellulosic biomass. Processes; 9. Epub ahead of print 1 July 2021. DOI: 10.3390/pr9071234.
[11] McMillan JD. Pretreatment of Lignocellulosic Biomass. 1994, pp. 292–324.
[12] Khan MFS, Akbar M, Xu Z, et al. A review on the role of pretreatment technologies in the hydrolysis
of lignocellulosic biomass of corn stover. Biomass and Bioenergy; 155. Epub ahead of print 1
December 2021. DOI: 10.1016/j.biombioe.2021.106276.
[13] Kang S, Fu J, Zhang G. From lignocellulosic biomass to levulinic acid: A review on acid-catalyzed
hydrolysis. Renewable and Sustainable Energy Reviews 2018; 94: 340–362.
[14] Lee JW, Jeffries TW. Efficiencies of acid catalysts in the hydrolysis of lignocellulosic biomass over
a range of combined severity factors. Bioresour Technol 2011; 102: 5884–5890.

[15] Kang S, Yu J. Effect of Methanol on Formation of Levulinates from Cellulosic Biomass. Ind Eng
Chem Res 2015; 54: 11552–11559.
[16] Girisuta B, Dussan K, Haverty D, et al. A kinetic study of acid catalysed hydrolysis of sugar cane
bagasse to levulinic acid. Chemical Engineering Journal 2013; 217: 61–70.
[17] Sajid M, Farooq U, Bary G, et al. Sustainable production of levulinic acid and its derivatives for fuel
additives and chemicals: Progress, challenges, and prospects. Green Chemistry 2021; 23: 9198–
9238.
[18] Fitzpatrick S. PRODUCTION OF LEVULINIC ACID FROM CARBOHYDRATE-CONTAINING

MATERIALS. 1997.
[19] Hayes DJ, Ross J, Hayes HB, et al. The Biofine Process: Production of Levulinic Acid, Furfural and
Formic Acid from Lignocellulosic Feedstocks. 2005.
[20] Brouwer T, Blahusiak M, Babic K, et al. Reactive extraction and recovery of levulinic acid, formic
acid and furfural from aqueous solutions containing sulphuric acid. Sep Purif Technol 2017; 185:
186–195.
[21] Alcocer-García H, Segovia-Hernández JG, Prado-Rubio OA, et al. Multi-objective optimization of

intensified processes for the purification of levulinic acid involving economic and environmental
objectives. Chemical Engineering and Processing - Process Intensification 2019; 136: 123–137.
[22] Solis-Sanchez JL, Alcocer-Garcia H, Sanchez-Ramirez E, et al. Innovative reactive distillation

process for levulinic acid production and purification. Chemical Engineering Research and Design
2022; 183: 28–40.
[23] Nhien LC, Long NVD, Kim S, et al. Design and Assessment of Hybrid Purification Processes through
a Systematic Solvent Screening for the Production of Levulinic Acid from Lignocellulosic Biomass.
Ind Eng Chem Res 2016; 55: 5180–5189.
[24] GFBiochemicals. Making Levulinic Acid Happen,

http://www.gfbiochemicals.com/_media/Document/2017/4/26/GF%20Low%20Quality.pdf (2016,
accessed 29 July 2022).
[25] Prescient & Strategic Intelligence. Levulinic Acid Market Research Report: By Technology (Biofine,
Acid Hydrolysis), Application (Food Additives, Pharmaceuticals, Agricultural Products, Personal
Care Products, Plasticizers, Fuel Additives) - Global Industry Analysis and Demand Forecast to
2030, https://www.psmarketresearch.com/market-analysis/levulinic-acid-market (2020, accessed 1
August 2022).

[26] Market Data Forecast. Levulinic Acid Market By Application (Pharmaceuticals, Agriculture, Food
Additives, Cosmetics), By Potential Downstream (Delta aminolevulinic acid (DALA), Diphenolic
Acid, Methyltetrahydrofuran (MTHF)) & By Region (North America, Latin America, Europe, Asia
Pacific, Middle East & Africa) - Industry Analysis on Size, Share, Growth, Trends & Forecast Report
| 2022 to 2027, https://www.marketdataforecast.com/market-reports/levulinic-acid-market (2022,
accessed 1 August 2022).
[27] Contreras-Zarazúa G, Martin-Martin M, Sánchez-Ramirez E, et al. Furfural production from

agricultural residues using different intensified separation and pretreatment alternatives. Economic
and environmental assessment. Chemical Engineering and Processing - Process Intensification;
171. Epub ahead of print 1 January 2022. DOI: 10.1016/j.cep.2021.108569.
[28] Fele L, Grilc V. Separation of furfural from ternary mixtures. J Chem Eng Data 2003; 48: 564–570.
[29] Errico M, Stateva RP, Leveneur S. Novel intensified alternatives for purification of levulinic acid
recovered from lignocellulosic biomass. Processes 2021; 9: 1–11.
[30] Mahida B, Benyounes H, Shen W. Process analysis of pressure-swing distillation for the separation
of formic acid–water mixture. Chemical Papers 2021; 75: 599–609.

View publication stats

LevulinicAcid Oct 2022

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

LevulinicAcid Oct 2022

Uploaded by

Copyright:

Available Formats

See discussions, stats, and author profiles for this publication at: https://www.researchgate.

Levulinic Acid Production from Cellulosic Biomass – Process Modeling and

Preprint · October 2022

Stoilas Stylianos Kontovas Nikiforos Misailidis

The user has requested enhancement of the downloaded file.

Stylianos Kontovas, Nikiforos Misailidis and Demetri Petrides

Figure 1. The molecular structure of levulinic acid (2D) [6]

Intelligen, Inc. Page 2

Biomass Pretreatment, Acid Hydrolysis and LA Production

Intelligen, Inc. Page 3

Intelligen, Inc. Page 4

Commercial Production of LA – the Biofine Process

Intelligen, Inc. Page 5

Levulinic Acid Purification – Downstream Processing

Intelligen, Inc. Page 6

Figure 4. Potential LA derivatives and applications. Source: [13].

Intelligen, Inc. Page 7

➢ Pretreatment and Reaction to LA (black icons)

Pretreatment and Reaction to LA

Table 2. Chemical composition of corn stover

Intelligen, Inc. Page 8

Reactions taking place in the PFR Conversion

Hemicellulose Hydrolysis (Mass Stoichiometry)

Hexoses to HMF (Molar Stoichiometry)

Pentoses to Furfural (Molar Stoichiometry)

HMF to Levulinic Acid (Molar Stoichiometry)

Reactions taking place in the CSTR Conversion

Cellulose Hydrolysis (Mass Stoichiometry)

Hemicellulose Hydrolysis (Mass Stoichiometry)

Furfural Formation (Molar Stoichiometry)

Intelligen, Inc. Page 9

Levulinic Acid Formation (Molar Stoichiometry)

Formic Acid Formation (Mass Stoichiometry)

Levulinic Acid Separation

Formic Acid Separation

Intelligen, Inc. Page 10

Virtual Heat Recovery

Intelligen, Inc. Page 11

4. EQUIPMENT SPECIFICATION AND FOB COST (2022 prices)

Intelligen, Inc. Page 12

Intelligen, Inc. Page 13

5. FIXED CAPITAL ESTIMATE SUMMARY (2022 prices in $)

5A. Total Plant Direct Cost (TPDC) (physical cost)

5B. Total Plant Indirect Cost (TPIC)

5C. Total Plant Cost (TPC = TPDC+TPIC)

5D. Contractor's Fee & Contingency (CFC)

5E. Direct Fixed Capital Cost (DFC = TPC+CFC)

Intelligen, Inc. Page 14

6a. MATERIALS COST - PROCESS SUMMARY

Unit Cost Annual Annual Cost

NOTE: Bulk material consumption amount includes material used as:

6b. LABOR COST - PROCESS SUMMARY

Unit Cost Annual Amount Annual Cost

6c. UTILITIES COST (2022 prices) - PROCESS SUMMARY

Unit Cost Annual Ref. Annual Cost

Intelligen, Inc. Page 15

7. EXECUTIVE SUMMARY (2022 prices)

Total Capital Investment 107,670,00 $

Intelligen, Inc. Page 16

Figure 6. Shortcut vs. Rigorous Physical State Calculation Toolbox Selection

➢ Normal Boiling Point

Intelligen, Inc. Page 17

Intelligen, Inc. Page 18