Journal of Cleaner Production 277 (2020) 124072

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Journal of Cleaner Production

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

Process synthesis and analysis of green plastic monomer production

from cellulose
Hyunwoo Kim a, 1, Julius Choi b, 1, Wangyun Won a, *
a
Department of Chemical Engineering, Kyung Hee University, 1732 Deogyeong-daero, Giheung-gu, Yongin-si, Gyeonggi-do 17104, Republic of Korea
b
Earth Energy Renewables, 6150 Mumford Rd, Bryan, TX 77807, USA

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

Article history: As a renewable building block, 2,5-furandicarboxylic acid (FDCA) is a potentially viable alternative to
Received 23 March 2020 petro-based terephthalic acid (TPA). For the commercialization of FDCA production, economically
Received in revised form feasible process development is crucial. In this study, we design a new catalytic conversion process for
30 August 2020
the production of the green plastic monomer (FDCA) and evaluate the economic feasibility of the process.
Accepted 31 August 2020
Available online 6 September 2020
In the proposed process, the FDCA is produced from cellulose using a bio-based green solvent composed
of gamma-valerolactone (GVL) and H2O via three-step conversion involving cellulose hydrolysis, glucose
Handling editor. Prof. Jiri Jaromir Klemes dehydration and 5-hydroxymethylfurfural (HMF) oxidation subsequently. For the efficient recovery of
solvents and products, the separation subsystem is designed and integrated with the conversion process.
Keywords: Moreover, to improve energy efficiency, a heat exchanger network combined with a heat pump is
Process design designed. The new process increases the FDCA productivity by 17% and reduces the total capital in-
Technoeconomic vestment by 52.6% after optimization. Furthermore, this proposed process leads to the minimum selling
Heat exchanger network price (MSP) of $1366/t for FDCA, which suggests that the proposed process for bio-based FDCA pro-
Polyethylene 2,5-furandicarboxylate
duction is a promising approach to substitute petro-based TPA ($1445/t). The sensitivity analysis iden-
Gamma-valerolactone
tifies that the main cost drivers are a feedstock price, steam price and discount rate, which should be
Ion exchanger
investigated for the further improvement of the economics of the process.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction ethylene glycol and petro-based terephthalic acid (TPA), due to

Lignocellulosic biomass is a renewable and abundant source in
nature that can be used to produce fuels (Won and Maravelias,
2017), value-added chemicals (Alonso et al., 2017), and polymers
(Sharma et al., 2019). Considerable efforts are being dedicated to
developing the economic process for the conversion of biomass to
bio-polymer to overcome dependence on the petro-based polymer
and several environmental issues derived from the traditional
fossil-based industry (Kucherov et al., 2018). Recently, several
polymers have been produced from biomass and commercially
available (Deng et al., 2015). In particular, bio-polyethylene tere-
phthalate (PET) has received substantial attention due to its similar
properties compared to petro-based counterparts PET (Xiao et al.,
2015). However, to date, many bio-PET is partially bio-based plas-
tic, which is produced by polymerization of biomass-derived
* Corresponding author.
E-mail address: wwon@khu.ac.kr (W. Won).
1
Equally contributed.
technical constraints (Chen et al., 2016). Fully biomass-derived
polymers like polylactic acid, polybutylene succinate, poly-
hydroxybutyrate, and polyglutamic acid have also been regarded as
an alternative to petro-based PET. However, the thermal, mechan-
ical, and barrier properties of these polymers are not competitive
with the petro-based counterpart. Therefore, we need to develop a
method for the production of fully bio-based polymers with
properties comparable to petro-based counterparts (Sajid et al.,
2018).
2,5-Furandicarboxylic acid (FDCA) is a promising renewable
building block for the production of polyethylene 2,5-
furandicarboxylate (PEF), which can likely replace conventional
petro-based PET, which is made of terephthalic acid (TPA), in some
applications (for instance, in water bottles and packaging) (Joshi
et al., 2019). Due to a similar structure between FDCA and TPA,
FDCA attracts attention as a bio-based monomer as a replacement
of TPA (Deng et al., 2015). PEF has attractive thermal and me-
chanical properties (Lam et al., 2018) as well as improved barrier
properties for O2 (Burgess et al., 2014a), CO2 (Burgess et al., 2015),

https://doi.org/10.1016/j.jclepro.2020.124072
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 H. Kim et al. / Journal of Cleaner Production 277 (2020) 124072
and H2O vapor (Burgess et al., 2014b). Despite these attractive
properties, to date, the commercial production of PEF has failed
owing to difficulties in economically producing high-purity FDCA
(Motagamwala et al., 2018). Therefore, the development of
economical production of high-purity FDCA is useful for commer-
cial processes.
Typically, FDCA can be produced via two routes: 1) catalytic
conversion of cellulose (Li et al., 2018), glucose (Huang et al., 2018a),
or fructose (Hou et al., 2016) to 5-hydroxymethylfurfural (HMF) and
2) oxidation of HMF to FDCA (Liguori et al., 2019).
Cellulose, which is a biopolymer that is composed of a glucose
unit, occupies the largest proportion of biomass, making up
approximately 40% (Motagamwala et al., 2016). It can be readily
hydrolyzed by using an acid catalyst (for instance, HCl, H2SO4, and
solid acid catalysts) or enzymes (for instance, cellulase) (Hegner
et al., 2010). Enzymatic hydrolysis is a useful method for the pro-
duction of glucose from cellulose because it can be processed under
mild conditions to achieve a high yield (Wang et al., 2014). How-
ever, there are potential problems with respect to capital and
operating costs, such as (1) the large reactor size resulting from a
long residence time, (2) maintenance of enzyme activity during the
reaction, and (3) recyclability of the enzyme due to its reuse in the
hydrolysis reaction.
Luterbacher et al. (2014) reported a new hydrolysis technology
for cellulose using biomass-derived gamma-valerolactone (GVL)
and H2O as the solvent. It included a dilute H2SO4 catalyst and
vertical counter-current flow reactor with a progressive increase in
temperature in which cellulose was converted to glucose in a 71.1%
yield. Here, the used H2SO4 catalyst can be easily removed by a
neutralization reaction using lime (Won et al., 2017).
Subsequently, glucose can be mainly converted to HMF by two
routes: (1) isomerization of glucose to fructose followed by dehy-
dration of fructose to HMF and (2) direct dehydration of glucose to
HMF (Tang et al., 2016). The former method is economically limited
to a 42% yield, which requires an additionally expensive separation
subsystem (Gallo et al., 2013), while the latter method can possibly
produce HMF at above 90% when using an ionic liquid (Gallo et al.,
2013). However, the latter method using an ionic liquid is not yet
commercially available owing to the expense of ionic liquids and
the deactivation problem caused by H2O (Zhang et al., 2018a). Li
et al. (2017) showed a direct glucose to HMF conversion strategy
by employing GVL and H2O as the co-solvent in combination with
HCl and NaCl as the catalyst and promoter, respectively, leading to a
62.5% HMF yield. In turn, HMF can be subsequently oxidized to
FDCA on a heterogeneous catalyst. FDCA has a low solubility in H2O,
leading to deposition of FDCA on the catalyst; thus, the use of a
heterogeneous catalyst is limited (Zhang et al., 2018b). Recently,
Motagamwala et al. (2018) reported that HMF could be oxidized to
FDCA using GVL and H2O as the co-solvent on a Pt/C catalyst in high
yield (93.6%). FDCA had a high solubility in GVL and H2O (5:5, mass
ratio), which enabled processing HMF at a high concentration
without the use of a homogeneous catalyst.
The potential bottleneck for commercialization of the process is
the design of a separation process for the purification and recovery
of final products. Several studies have been carried out that pro-
duced high-purity FDCA from renewable sources by proposing new
separation processes (Bello et al., 2020). In these studies, they
typically employed several solvents for different reaction steps to
produce FDCA, resulting in problems, such as an increase in sepa-
ration costs or process complexity. Therefore, in this study, we
investigated the effect of the use of identical solvents (GVL and
H2O) on the separation subsystem cost and process complexity.
Furthermore, to our knowledge, there are few studies that have
designed process starting from cellulose to FDCA that employed the
same solvents in each conversion reaction.
Consequently, the objective of this study was to achieve three
catalytic conversions: 1) hydrolysis of cellulose to glucose, 2)
dehydration of glucose to HMF, and 3) oxidation of HMF to FDCA
with effective separation and recovery subsystems that handle the
challenges mentioned above. In addition, the determination of the
economic feasibility of the proposed process was conducted via
technoeconomic analysis to suggest the direction of future funda-
mental experimental research in this field.
2. Technology overview
In this study, the proposed conversion process included three
catalytic conversion reactions: 1) biomass-derived cellulose to
glucose via hydrolysis, 2) glucose to HMF via dehydration, and 3)
HMF to FDCA via oxidation. The major reaction pathway and con-
ditions are shown in Fig. 1 and Table 1. Furthermore, effective
separation subsystems were designed to recover and recycle GVL,
H2O, and HCl in each reaction and to purify and recover FDCA and
activated carbon for sale as individual products.
2.1. Conversion of cellulose to HMF via glucose
Luterbacher et al. (2014) showed that glucose could be obtained
from cellulose (4.8 wt% loading in solvent) in a 71.1% yield via hy-
drolysis using GVL and H2O as the co-solvent (4:1 mass ratio) with a
dilute H2SO4 catalyst (5 mM) within 0.5 h in a vertical counter-
current flow reactor. In this reactor, the liquid stream flows
through the solids, which are advancing in the opposite direction
with a progressive increase in temperature (from 430 K to 490 K).
Cellulose could also be decomposed to humins, levulinic acid (LA),
formic acid (FA), and HMF in 14.7%, 9.3%, 9.3%, and 4.9% yields,
respectively. The use of GVL is likely to solubilize cellulose and its
derivatives (LA, FA, HMF, and humins); consequently, the glucose
yield is improved compared to a control experiment without GVL
(Luterbacher et al., 2014). Moreover, biomass-derived LA can be
converted to GVL in a 99.0% yield via hydrogenation on a RuSn4/C
catalyst at 483 K and 35.5 atm (Wettstein et al., 2012), thus
replenishing the GVL requirement during the process.
Li et al. (2017) showed that glucose (3 wt% loading in solvent)
could be converted to HMF with a 62.5% yield, via dehydration
using GVL and H2O as the co-solvent (4:1 mass ratio), with HCl as
the catalyst (0.2 M) and NaCl (0.1 M) as the promoter; the reaction
was performed for 1 h at 413 K and 20.0 atm. Through the dehy-
dration, glucose was also converted to humins, LA, and FA with
19.3%, 18.2%, and 18.2% yields, respectively. In particular, HCl led to a
higher conversion yield and increased selectivity toward HMF,
compared with H2SO4 at a lower temperature (413 K), resulting in
heat energy savings. Moreover, the addition of NaCl (0.1 M) in HCl
(0.2 M) led to an increase in the HMF yield up to 62.5%. However,
the excessive amount of NaCl may increase the rehydration of HMF
to LA.
2.2. Conversion of HMF to FDCA
Motagamwala et al. (2018) demonstrated the conversion of HMF
(7.5 wt% in solvent) to FDCA via oxidation using GVL and H2O as the
co-solvent (5:5 mass ratio) on a Pt/C catalyst at 40 atm and 383 K; a
93.6% yield of FDCA was obtained. The aforementioned study re-
ported that HMF was also transformed to the polymer with a 6.3%
yield and could be further adsorbed in an adsorption bed packed
with activated carbon. Here, the adsorbed components (humins,
polymer, etc.) were converted to additional activated carbon via
burning during the regeneration of the bed using O2.
In this reaction, owing to the high solubility of products in the
GVL and H2O co-solvent, catalyst clogging is likely to be avoided,
 H. Kim et al. / Journal of Cleaner Production 277 (2020) 124072 3

Fig. 1. Schematic diagram of the proposed process.

leading to the elimination of waste handling treatment for the in- The cost of the entire process (glucose production, HMF production,
ternal reactor and catalysts. FDCA production, FDCA separation, and solvent recovery) was
Moreover, the high solubility of FDCA in the solvent makes it estimated using an Aspen Process Economic Analyzer (Kim et al.,
possible to oxidize HMF to FDCA at high concentrations on a het- 2020a) and the exponential scaling expression used in the Na-
erogeneous catalyst owing to less deposition of FDCA on the tional Renewable Energy Laboratory (NREL) report (Davis et al.,
catalysts. 2015). The other subsystems (wastewater treatment, storage, and
utilities) were estimated using an exponential scaling expression
(Ramapriya et al., 2018) based on the equipment size and cost data
2.3. Separation subsystem
in the NREL (Davis et al., 2015). The heat exchanger network was
designed using the Aspen Energy Analyzer for reducing energy
H2SO4 can be removed by the addition of Ca(OH)2, and then the
requirements (Choe et al., 2020). The processing rate was assumed
generated CaSO4,2H2O can be disposed of. Humins, HMF-derived
to be 900 tons of cellulose per day, which is equivalent to 2000 dry
polymer, and FA can be adsorbed on activated carbon to purify
tons of lignocellulosic biomass per day (Davis et al., 2015). All
HMF. Following adsorption, the adsorption bed is regenerated us-
equipment and raw material costs used in the entire process were
ing O2, where some proportion of carbon in humins, polymer, and
indexed to the common base year of 2015 using the Chemical En-
FA (57.2%) is converted to activated carbon (Motagamwala et al.,
gineering’s Plant Cost Index (from Chemical Engineering
2018). The produced activated carbon is partially reused for
Magazine). The minimum selling price (MSP) of FDCA was deter-
further adsorption, and the remaining is sold as an individual
mined using a discounted cash flow analysis (Davis et al., 2015)
product.
based on several economic parameters and assumptions (see
HCl has a low boiling point comparing to HMF, glucose, and GVL.
Supplementary Material).
Therefore, it can be easily separated using a distillation column for
reuse in the reaction. GVL and H2O can be separated from HMF
3.2. Process design
using distillation columns for reuse and optimization of the further
feed stream concentration. An ion exchanger can be used to remove
We developed the integrated process based on the technologies
mineral salts (for instance, NaCl), which deactivate the catalyst
mentioned in Section 2, for the production of green plastic mono-
during the following catalytic conversion (Davis et al., 2015). FDCA
mer (FDCA) and activated carbon from biomass-derived cellulose.
solubilized in the GVL and H2O co-solvent can be crystallized by
The integrated process consists of eight subsystems: 1) glucose
cooling the products to 298 K so that FDCA can be collected using a
production, 2) HMF production, 3) FDCA production, 4) FDCA
solideliquid separator.
separation, and 5) solvent recovery, as well as (6) wastewater
treatment, (7) storage, and (8) utilities. Fig. 2 shows a flow diagram
3. Process development for the proposed process. The stream information with respect to
Fig. 2 is listed in the Supplementary Material.
3.1. Simulation and assumptions
3.2.1. Glucose production
A process model was developed based on experimental data. The raw cellulose (stream 1), which is a solid, is directly injected
Table 1
into a glucose conversion reactor (R-1) that was designed as a
Reaction yields and conditions for each reactor. vertical countercurrent reactor along with H2SO4 (stream 2) and
recycled GVL and H2O (stream 3). In this reactor, cellulose is con-
Reactor Reaction Yield Condition Catalyst Solvent
verted to glucose via hydrolysis in a 71.1% yield as well as HMF (4.9%
R-1 Cellulose/Glucose 71.1% 430 K, H2SO4 GVL, H2O (4:1) yield). Following conversion of cellulose to glucose, the H2SO4 used
Cellulose/HMF 4.9% 20.4 atm
as the catalyst was removed in a neutralizer (R-2) using Ca(OH)2
Cellulose/LA þ FA 9.3%
Cellulose/Humins 14.7% (stream 6), and the generated CaSO4,2H2O (gypsum) was disposed
R-3 Glucose/HMF 62.5% 413 K, HCl GVL, H2O (4:1) of (stream 7).
Glucose/LA þ FA 18.2% 20.0 atm
Glucose/Humins 19.3%
3.2.2. HMF production
R-4 HMF/FDCA 93.6% 383 K, Pt/C GVL, H2O (5:5)
HMF/Polymer 6.3% 40.0 atm The liquid stream (stream 10) containing glucose from the
R-5 LA/GVL 99.0% 483 K, RuSn4/C neutralizer (R-2) is injected into the HMF conversion reactor (R-3)
LA/2-MBAa 1.0% 35.5 atm with the HCl catalyst (stream 56) and NaCl (stream 11). Then, the
FA/H2þCO2 100% glucose is converted to HMF with a 62.5% yield, as well as LA (18.2%)
a
2-MBA: 2-methylbutyraldehyde and humins (19.3%). The generated humins and recycled polymer
4 H. Kim et al. / Journal of Cleaner Production 277 (2020) 124072
Fig. 2. Process flow diagram for the proposed process. FDCA, 2,5-furandicarboxylic acid; FA, formic acid; GVL, gamma-valerolactone; HMF, 5-hydroxymethylfurfural; LA, levulinic
acid.
(produced from HMF via polymerization in R-4) are converted to
activated carbon via adsorption on activated carbon in the
adsorption bed (S-1). The 57.2% of carbon in humins, polymer, and
other biomass residues are converted to activated carbon (stream
14) during the regeneration of the adsorption bed using O2 (stream
13), while the remainder (42.8% of carbon) is converted to CO2
(stream 15). Following adsorption, the liquid stream (stream 17) is
routed to continuously linked distillation columns (D-1, D-2, and D-
3) to adjust the solvent-to-biomass ratio of each reactor (R-1, R-3,
and R-4). The function of D-1 is to recover H2O and HCl for reuse in
the HMF conversion reactor (R-3), that of D-2 is to recover and
recycle H2O to the glucose conversion reactor (R-1), and that of D-3
is to recover GVL, except for the amount of GVL required for the
FDCA conversion reactor (R-4). Following the separation of GVL,
H2O, and HCl, the liquid stream (stream 30) produced at the bottom
of the distillation column (D-3) is routed to an ion exchanger (S-1)
to remove soluble cations and anions to prevent catalyst deacti-
vation during the subsequent conversion of HMF to FDCA (R-4). In
the ion exchanger (S-1), soluble Naþ and Clþ are detached in an
anti-charged resin packed in the ion exchanger (S-1), and these are
removed during the regeneration by using HCl (stream 31) and
NaOH (stream 32).
3.2.3. FDCA production
After the ion exchange operation, the purified liquid stream
(stream 34) containing HMF is injected into the FDCA conversion
reactor (R-4) with H2O (stream 35) and O2 (stream 37). Here, HMF is
converted to FDCA via an oxidation reaction at a 93.6% yield using
the GVL and H2O co-solvent. In this reaction, the remaining HMF is
converted to polymer, which is further adsorbed on activated car-
bon after the solvent recovery subsystem.
3.2.4. FDCA separation
To crystallize the FDCA, the liquid stream (stream 38) is cooled
to 298 K (stream 39) using a cooler (C-2); thus, the crystallized
FDCA (stream 41) is separated from the liquid (stream 39) in the
solideliquid separator (S-3), and it is sent to a second solideliquid
separator (S-4) for further purification by adding H2O (stream 42)
following evaporation (S-5) and cooling (C-3) of H2O. In the second
solideliquid separator (S-4), purified FDCA (up to 99.5%) is pro-
duced (stream 43).
3.2.5. Solvent recovery
The liquid stream (stream 40) from the solideliquid separator
(S-3) is sent to a distillation column to remove excess H2O (stream
49). Following the separation of excess H2O, the stream produced at
the bottom of the column (D-4) is split, and some proportion
(19.0%, stream 53) is sent to the GVL conversion reactor (R-5),
where LA is converted into GVL via a hydrogenation reaction using
H2 (stream 52), while the other portions (stream 51) are directly
sent to a vessel (V-1). Finally, the collected GVL, H2O, and polymer
(stream 55) are recycled back for HMF production for reuse in each
reaction.
3.3. Heat integration
In this proposed process, the low and different biomass loadings
in the solvent per each reactor are the major bottlenecks, leading to
a significantly high utility requirement to separate the solvent.
When 900 tons of cellulose are processed per day in the proposed
process, the total heating requirement is 399.1 MW. The most
energy-intensive unit is the distillation column (D-2, 145.1 MW)
because large amounts of H2O should be separated for reuse in R-1
and R-3 and to regulate the HMF loading in the solvent (7.5 wt%) for
the following reaction.
However, during this process, heat and electricity should be
supplied from an external source owing to the absence of heat and
power generation, which is because the humins and other biomass
residues were all consumed when the individual product was
produced (activated carbon). Therefore, the significantly large
amount of external source (for instance, steam) is required to
satisfy the heating requirement of this process.
To tackle this challenge, we performed heat integration by
exchanging energy between hot and cold streams (Park et al., 2019).
Moreover, we introduced a heat pump (CP-1, see Fig. 2) at the top of
the distillation column (D-2) to utilize the discharged heat energy
following compression (stream 22) and cooling the vapor stream
(stream 23) (Lee et al., 2019). After heat integration, we could
 H. Kim et al. / Journal of Cleaner Production 277 (2020) 124072 5

recover large amounts of energy (239.8 MW), leading to a large
reduction in utility costs (Fig. 3). By introducing a heat pump,
101.0 MW of heat energy could be generated, covering several units
that require heat energy. The heat curve corresponding to this
result is shown in the Supplementary Material.
4. Results and discussion
4.1. Capital and operating costs
The capital and operating costs were calculated based on the
equipment and raw material costs shown in Table 2. Here, we
compare the proposed process (strategy A) with a previous study
(strategy B, Kim et al., 2020b) in which cellulose was directly con-
verted to HMF using tetrahydrofuran (THF) and H2O as the co-
solvent without intermediates (such as glucose in our process).
The total installed equipment costs for strategies A and B were
calculated to be $75.3#106 and $154.2#106, respectively. The major
installed equipment cost is provided in Supplementary Material.
The total installed equipment cost of strategy A was lower than that
of strategy B by $78.9#106, despite the additional conversion step
and separation units for the production of HMF in strategy A. The
main reason for this is that the reactor cost for the production of
HMF in strategy B (HMF conversion reactor: $91.1#106) is consid-
erably higher than in strategy A (glucose conversion reactor:
$2.2#106, HMF conversion reactor: $4.1#106). However, the
installed equipment cost of other subsystems (FDCA production,
FDCA separation, solvent recovery, wastewater treatment, storage,
and utilities) for strategy A is slightly higher ($1e3#106) than that
for strategy B, primarily owing to the increased solvent require-
ment resulting from improved FDCA productivity compared with
strategy B (strategy A: 129,366 t/yr and strategy B: 110,276 t/yr).
The total capital investments for strategies A and B, which are the
sums of the total direct cost, indirect cost, land, and working capital,
were calculated to be $142.7#106 and $300.1#106, respectively (see
Supplementary Material).
The total operating cost of strategy A was calculated to be
$212.0#106/yr, which is higher than that of strategy B ($189.2#106/
yr) by $22.8#106/yr. This difference is mainly attributed to the high
steam cost of strategy A resulting from the large amount of heating
required and regeneration costs for the ion exchanger used for HCl
($2.4#106/yr) and NaOH ($8.7#106/yr). The feedstock cost accounts
for the largest proportion of total operating costs for the two
strategies (strategy A: 58.0% and strategy B: 64.9%). Regarding the
cost of the Pt/C catalyst, strategy A was higher than strategy B by
$2.2#106/yr mainly owing to increased HMF productivity resulting
from direct HMF production from cellulose during glucose pro-
duction (see R-1 in Table 1).

4.2. Minimum selling price

Based on the capital and operating costs, MSP of FDCA was

calculated using discounted cash flow analysis (see Supplementary
Material). Fig. 4 shows a comparison of costs and revenues for the

Fig. 3. Results of the energy requirements before and after heat integration. Outer and
inner circles refer to the energy requirement before and after heat integration, Fig. 4. Comparison of costs and revenues for the different strategies. ROI, return on
respectively. investment.

Table 2
Comparison of the capital and operating costs of strategies A and B.

Capital costs ($106) Operating costs ($106/yr)

Components Strategy A Strategy B Components Strategy A Strategy B

Glucose production 5.7 Feedstock 122.9 122.9

HMF production 29.2 121.5 THF makeup 10.1
FDCA production 10.8 10.3 O2 makeup 4.9 5.0
FDCA separation 5.6 2.9 Pt/C catalyst 14.6 12.4
Solvent recovery 1.4 1.2 Other raw materialsa 13.4 2.8
Wastewater treatment 11.0 9.7 Disposal of gypsum 0.3 0.9
Storage 3.6 3.5 Steam 44.4 16.2
Utilities 7.9 5.0 Cooling H2O 1.6 0.9
Electricity 5.0 9.7
Fixed operating costs 4.9 8.4
Total installed equipment cost 75.3 154.2 Total operating costs 212.0 189.2
a
Other raw materials include HCl, NaCl, NaOH, H2SO4, Ca(OH)2, RuSn4/C, H2, wastewater chemicals, and cooling tower chemicals.
6 H. Kim et al. / Journal of Cleaner Production 277 (2020) 124072
different strategies. The MSP of FDCA for strategy A was calculated
to be $1366/t, which is lower than the MSP of strategy B ($1532/t)
by $166/t. By comparing the different strategies, we observed that
the increase in FDCA productivity and decrease in capital cost
resulting from the absence of an expensive reactor (cellulose to
HMF conversion) had a positive impact on the MSP of FDCA, leading
to a decrease in MSP from $1532/t to $1366/t despite additional
conversion (conversion of cellulose to glucose) and separation
subsystems (distillation columns and ion exchanger).
The cost contributions for the two different strategies are shown
in Fig. 5. For both strategies A and B, feedstock cost was the highest
cost contributor contributing $950/t (52.9% of the total cost) and
$1114/t (53.4% of the total cost) to the MSP of FDCA, respectively.
Among the subsystems, HMF production was the highest cost
contributor (strategy A: 25.3% of the total cost and strategy B: 35.9%
of the total cost) for both strategies owing to the considerable
steam cost ($44.4#106/yr) and the high cost of the reactor for cel-
lulose to HMF conversion ($91.1#106). The other subsystems have
insignificant effects on the MSP of FDCA, contributing to less than
10% of the total cost.
4.3. Sensitivity analysis
A single-point sensitivity analysis was performed using eco-
nomic and process parameters based on strategy A. Each variable
was increased or decreased by 25% while the other variables were
held constant. The sensitivity of FDCA on the MSP is shown as a
tornado chart in Fig. 6. Among the variables, the feedstock price
most affects the MSP of FDCA, contributing to an increase and
decrease of MSP to $1603/t and $1128/t, respectively, from $1366/t
when the feedstock price fluctuates by 25% ($338e563/t). It is re-
ported that cellulose could be obtained from various source with
different prices, such as grasses ($45e170/t), wood ($450e500/t),
and jute fiber ($390e780/t) (Keijsers et al., 2013), which means that
the range of a cellulose price in this sensitivity analysis is relevant.
In the United States, the annual production of lignocellulosic
biomass is approximately 1.25#109 t, where forest biomass oc-
cupies 30% proportion (Paul and Dutta, 2018). We assume that the
cellulose is obtained from the birch tree which is 4% of forest
biomass based on the report from Wisconsin Department of
Fig. 5. Cost contribution per subsystem ($/t) for strategies A and B. The total cost of strategy A ($1796.0/t) also includes wastewater treatment (capital: $23.1/t, operating: $3.6/t),
storage (capital cost: $7.6/t, operating cost: $1.2/t), and utilities (capital cost: $16.6/t, operating cost: $3.5/t).
Natural Resources (Paper birch report, 2019), meaning that there is
a sufficient amount to further production of cellulose to make the
assumption of plant capacity (2000 t/day of biomass) sufficiently
feasible. The next sensitive variable is the steam price, contributing
to a decrease in the MSP to $1279/t when steam prices decrease by
25% owing to the large amount of steam required in the proposed
process. However, the catalyst regeneration period increases to
$1404/t as it decreases by 25% owing to increased catalyst costs
resulting from more frequent regeneration of the catalyst.
Beyond the variables related to variable operating costs, the
discount rate also has a heavy impact on the MSP of FDCA. When
the discount rate is increased by 25%, the MSP of FDCA is increased
to $1393/t. However, the tax rate, equity, electricity price, O2 price,
and cooling H2O price have less of an effect on the MSP of FDCA
than other variables, contributing to less than a 1% change in the
MSP of FDCA.
Through the sensitivity analysis, the feedstock price is pointed
out as the most significant cost driver. Therefore, we should further
investigate the selection of less expensive feedstock or the efficient
utilization of feedstock with the same or improved performance.
Regarding the selection of cheap feedstock, organic waste could be
an attractive feedstock in exchange of the expensive cellulose for
the production of bio-based monomer (Volanti et al., 2019). There
are several types of organic waste including municipal solid waste,
manure, sewage sludge, lignin, and residues from fruit and food
waste (Pagliano et al., 2017). A significant amount of organic waste
is produced annually at a less expensive price (Badgett et al., 2019).
However, the variability in the quality and composition inhibits the
development of technological and economical feasible conversion
processes (Coma et al., 2017). Therefore, for the realization and
commercialization of organic waste utilization, further investiga-
tion on the development of efficient technologies handling the
mentioned issues is indispensable. Furthermore, to improve the
efficiency of lignocellulosic biomass utilization, the proposed pro-
cess using cellulose could be incorporated with other value-added
fuels and chemicals production utilizing hemicellulose and lignin,
which could lead to significant improvement of economics (Huang
et al., 2018b). The other main cost drivers are steam price and
discount rate. Further investigation regarding heat exchanger net-
works for a reduction in steam requirement is required to improve
 H. Kim et al. / Journal of Cleaner Production 277 (2020) 124072
Fig. 6. Single-point sensitivity tornado chart of the economic parameters in the proposed process.
the economics of the process.
5. Conclusions
A new process for the production of FDCA, as a renewable
building block for the replacement of petro-based TPA, from cel-
lulose was developed. Effective separation subsystems for recov-
ering and recycling solvents and purifying products were designed.
Heat integration, combined with a heat pump, successfully reduced
the energy requirement by up to 60%. The technoeconomic analysis
revealed that The MSP of FDCA for the proposed process was
determined to be $1366/t. This result suggests that this process
could become an economically feasible process in place of the
petro-based TPA ($1445/t) production process. The sensitivity
analysis suggests that we need further investigation on the selec-
tion of less expensive feedstocks and the design of an improved
heat exchanger network for the further economic improvement of
the process. Furthermore, the economics of the proposed process
utilizing cellulose as the sore carbon source could be enhanced by
being incorporated with hemicellulose and lignin-derived fuels and
chemical production. Finally, successful product development is
crucial for the success of the commercialization of this process.
Therefore, the test of the properties of the final product derived
from FDCA is required.
CRediT authorship contribution statement
Hyunwoo Kim: Methodology, Formal analysis, Writing - orig-
inal draft, Writing - review & editing. Julius Choi: Validation,
Writing - original draft, Writing - review & editing, Visualization.
Wangyun Won: Supervision, Project administration, Funding
acquisition, Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgement
This work was supported by the National Research Foundation
of Korea (NRF) grant funded by the Korean government (MSIT) (No.
7
2018R1C1B6009074). W. Won would like to acknowledge the
financial support from C1 Gas Refinery Program through the Na-
tional Research Foundation of Korea funded by the Ministry of
Science ICT and Future Planning (2015M3D3A1A01064929).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2020.124072.
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