Energy 175 (2019) 546e553

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Energy
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Catalytic conversion of corn stover for 〈gamma〉-valerolactone

production by two different solvent strategies: Techno-economic
assessment
Jaewon Byun a, Jeehoon Han a, b, *
a
School of Semiconductor and Chemical Engineering, Chonbuk National University, 567 Baekje-Daero, Deokjin-gu, Jeonju, 54896, South Korea
b
School of Chemical Engineering, Chonbuk National University, 567 Baekje-Daero, Deokjin-gu, Jeonju, 54896, South Korea

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

Article history: This study compares two processes to produce g-valerolactone from lignocellulosic biomass: Process A is
Received 12 October 2018 single processing of cellulose by using lignin-derived propyl guaiacol solvent; Process B is simultaneous
Received in revised form processing of cellulose and hemicellulose by using g-valerolactone solvent derived from cellulose and
23 February 2019
hemicellulose. Large-scale processes that integrate conversion and separation technologies are assem-
Accepted 11 March 2019
Available online 14 March 2019
bled based on experimental data, and daily GVL productions are 98 tonnes (Process A) and 375 tonnes
(Process B). A heat-exchanger network is designed to reduce heating requirements, and the energy ef-
ficiencies are 13.3% (Process A) and 37.3% (Process B). Techno-economic assessment is conducted to
Keywords:
Lignocellulosic biomass
identify the economic feasibility. The minimum selling price of g-valerolactone for Process A (US$ 2.36/
g-Valerolactone kg) and Process B (US$ 0.88/kg) are comparable with market price. The difference in the minimum selling
Propyl guaiacol prices is mainly caused by effective utilization of the hemicellulose in lignocellulose biomass in Process B.
Catalytic conversion Sensitivity analyses present that changes in key parameters could not reverse the minimum selling price
Process synthesis of g-valerolactone between the two strategies, but the conversion of xylose to value-added chemical in
Economic feasibility Process A makes this possible. This study shows that development of conversion technologies to effec-
tively utilize the hemicellulose in lignocellulosic biomass is critical to improve process economics.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction absence of SA, then used in LA production [16]. PG is hydrophobic

Conversion of lignocellulosic biomass (LB) can yield valuable
fuels and chemicals [1e3]. g-Valerolactone (GVL) is the most
attractive LB derivative; GVL is used in synthesis of fuels, food ad-
ditives, solvents, and polymers [4e6]. LB contains 15e30% lignin,
20e35% hemicellulose (C5), and 30e50% cellulose (C6) [1,7]. The C5
or C6 in LB can be converted to GVL by hydrolysis and dehydration
to levulinic acid (LA) under homogeneous and heterogeneous cat-
alysts [8e11], then hydrogenation of the LA under heterogeneous
catalysts [12e15].
A homogeneous catalytic process can be used to hydrolyze and
dehydrate C6 to LA over dilute sulfuric acid (SA) catalyst [12].
Subsequently, C6-derived LA can be converted to GVL over a RuSn
heterogeneous catalyst by using propyl guaiacol (PG) solvent in the
* Corresponding author. School of Chemical Engineering, Chonbuk National
University, 567 Baekje-Daero, Deokjin-gu, Jeonju, 54896, South Korea.
E-mail address: jhhan@jbnu.ac.kr (J. Han).
lignin derivatives, and can be used as an extractive solvent to
separate LA from the aqueous solution that contains SA. The key
challenge of this process is to effectively fractionate LB to achieve
high yields of C6 for LA production and lignin for PG production.
GVL can be used as a reaction solvent in biomass processing due
to the high solubility of biomass components and products in the
presence of GVL [5]. A three-step catalytic process in the presence
of solubilized lignin using GVL solvent can convert C5 and C6
simultaneously to GVL with high yields [9]. The first step is a ho-
mogeneous reaction step that uses dilute SA catalyst that convert C5
to furfural (FF) and C6 to LA. The second step is a heterogeneous
reaction step that uses bimetallic and acid (PtSn/SiO2 and Amber-
lyst 70) catalysts to convert FF to LA in the presence of LA produced
and in the absence of SA used in C5 and C6 conversion. The third
step is conversion of the LA to GVL over a RuSn heterogeneous
catalyst in the presence of GVL solvent. The process uses large
amounts of LB-derived GVL as a reaction solvent, and therefore has
production loss and sizing burden. But it has simplified separation
steps in biomass processing, also eliminating pretreatment.

https://doi.org/10.1016/j.energy.2019.03.070
0360-5442/© 2019 Elsevier Ltd. All rights reserved.
 J. Byun, J. Han / Energy 175 (2019) 546e553
Nomenclature
ACC Annualized capital cost, US$/y
AOC Annualized operating cost, US$/y
C6 Cellulose
CS Corn stover
FA Formic acid
FF Furfural
FFA Furfuryl alcohol
GVL g-Valerolactone
HEN Heat exchanger network
C5 Hemicellulose
IRR Internal rate of return, %
LA Levulinic acid
Feasibility of biorefinery system is evaluated in two aspects,
environmental impacts and techno-economics. Table 1 shows the
difference between the two methodologies. Environmental impacts
of bioproducts are quantified by life cycle assessment (LCA) that
considers all the stages of a product's life from raw material pro-
curement and manufacture to use and disposal [17]. Previous
studies performed the LCA of biorefinery and compared with pe-
troleum refinery [18]. In most cases focused the global warming
potential and fossil depletion, biorefineries are more environ-
mentally preferable than petroleum refineries [19e21]. Techno-
economic assessment (TEA) analyzes the technical and economic
performance of biorefinery system and determines the minimum
selling price (MSP) of bio-products by considering the manufacture
[22e24]. Unlike the results of environmental assessment, the eco-
nomics of biorefinery are commonly less favorable than those of
petroleum refineries [25,26]. Considering the above, TEA may be
more significant than LCA to evaluate the feasibility of biorefinery
system. We conduct TEA study on two strategies for producing GVL,
and it can suggest feasible strategy for sustainable GVL production.
In this work, two processes using different solvents to produce
GVL from LB are assembled at a large scale. Process A converts C6 by
using lignin-derived PG solvent. Process B simultaneously pro-
cesses C5 and C6 by using GVL solvent derived from C5 and C6.
Simulation model for each process is developed based on the
experimental data. Then economics of both processes are evaluated
in terms of the unit production cost of GVL, and the major cost
contributors are compared in the process by cost breakdown. The
goal of this study is presenting techno-economic feasibilities of two
processes and determining techno-economic bottlenecks of LB-
based GVL production strategies. This study suggests a new
research direction to increase possibility of commercializing LB-
based GVL production strategy. The following sections cover
simulation methods and results for large-scale synthesis and eco-
nomic evaluation of two processes for the catalytic production of
GVL from LB.
2. Methods
Two processes for the production of GVL from LB are assembled
Table 1
Comparison of LCA and TEA studies on biorefinery.
LCA
Goal Quantifying environmental impacts
System boundary Raw material procurement, manufacture, use, and disposal
Major results Global warming potential and fossil depletion
547
LB Lignocellulosic biomass
LCA Life cycle assessment
MA Maleic anhydride
MC Net manufacturing cost, US$/y
MSP Minimum selling price, US$/kg
MW Megawatt
MWe Megawatt-equivalent, MW
PFD Process flow diagram
PG Propyl guaiacol
SA Sulfuric acid
TEA Techno-economic assessment
TC Total cost, US$/y
TR Total revenue, US$/y
WWT Wastewater treatment
at a large scale by using nth plant analysis with the following as-
sumptions. 1) The process can be scaled up based on the experi-
mental results (yields and selectivities) without a performance loss.
2) The process parameters (temperature, pressure, composition,
reaction time, etc.) are set equal to the experimental conditions. In
this work, a biorefinery plant processing 2000 dry tonnes (t) of corn
stover (CS) per day was considered, and the compositions and ca-
pacity of the processed LB were selected to be consistent with the
previous studies [13,27,28]. Fig. 1 shows the process flow diagram
(PFD) of two processes for producing GVL from LB.
2.1. Process A: production of GVL from the single processing of C6 by
using lignin-derived PG solvent
The PFD of Process A outlines the production of GVL by pro-
cessing of C6 by using lignin-derived PG solvent. Process A can be
broken into eight main systems: biomass handling, pretreatment,
LA production, GVL production, PG production, wastewater treat-
ment (WWT), heat and electricity generation, and storage (Fig. 1a).
Simulation models of major units for three main systems (LA pro-
duction, GVL production, and PG production) in the Process A were
developed by using the ASPEN Plus Process Simulator [29]; the
other systems were designed based on simulation results in pre-
vious studies [13,27,28].
LB is shredded in the biomass handling system, then C5 in a
liquid mixture (stream 1) is hydrolyzed to xylose with 92.5% molar
yield, in a mixture of 30 wt% CS with dilute 1.1 wt% SA at 463 K and
12.2 bar in the pretreatment hydrolyzer (R-1, Fig. 1a) [22]. After C5
hydrolysis, the resulting stream is sent to the pressure filter (S-2,
Fig. 1a) to recover insoluble component (C6 and lignin) for the
subsequent system (LA production). The solid stream (stream 3,
Fig. 1a) obtained from S-1 is sent to LA production, while the
remaining liquid stream containing soluble xylose and SA is sent to
the separator (S-2, Fig. 1a) for removal of SA by neutralization and
precipitation using Ca(OH)2. Then, the soluble xylose stream
(stream 4, Fig. 1a) is sold as commercial grade liquor after
concentrating up to 460 g/L (40 wt%). C6 is hydrolyzed and dehy-
drated in the aqueous phase reactor (R-2, Fig. 1a) that contains
28.1 wt% C6 and 0.5 M SA catalyst at 423 K and 35 bar to produce LA
TEA
Analyzing technical and economic performance
Manufacture
Cost, revenue, minimum selling price, and internal rate of return
548 J. Byun, J. Han / Energy 175 (2019) 546e553
Fig. 1. PFD of two processes to convert LB to GVL.
and formic acid (FA) with 52% molar yields [12]. Insoluble products
that contain 55 wt% lignin and humins (stream 11, Fig. 1a) are
separated from the aqueous mixture by pressure filtration (S-3,
Fig. 1a) with the addition of H2O (H2O/feed mass ratio ¼ 1.16), then
fed to the PG production system. The resulting products in the
solubilized stream are fed to the extractor (S-4, Fig. 1a) at 298 K, to
partition 41.1% LA (with 7.5% FA) to the organic (PG) phase in a PG/
aqueous solution mass ratio ¼ 1 (stream 16, Fig. 1a) for the subse-
quent system (GVL production); the SA and remaining components
in the aqueous phase (stream 12, Fig. 1a) are returned to the LA
production system.
LA is hydrogenated over 5 wt% RuSn(1:4)/C catalyst in the
packed bed flow reactor (R-3, Fig. 1a) that contains 10.0 wt% LA in
PG solution at 453 K and 13.8 bar to produce GVL with 93% molar
yield [16]. The PG-rich mixture (stream 19, Fig. 1a) that contains
1.7 wt% GVL is sent directly to two distillation columns (D-1: 30-
stage, D-2: 14-stage) in series for purification. PG (stream 21,
Fig. 1a) is obtained at the bottom of D-1 at 618 K and 1 bar and is
then recycled to the LA production system. The top liquid stream of
D-1 is further distilled to obtain 99 wt% GVL at the bottom of D-2 at
479 K, then sent to product storage (stream 23, Fig. 1a). The distil-
lation top liquid (stream 22, Fig. 1a), consists mainly of H2O and
other trace byproducts, and is sent to the WWT system.
Following the GVL production system, PG losses are small
(0.01%). For PG production, the lignin-rich stream containing 45 wt
% H2O is converted to PG (12.5%) and other trace byproducts
(guaiacyl propanol (GP, 13.8%), propyl syringol (PS, 1.3%), and
syringyl propanol (SP, 0.3%)) at 4 MPa in a H2-rich environment and
473 K with 28% total molar yield over a 0.45 wt% Pt black catalyst in
a one-pot reactor (R-4, Fig. 1a) that contains 9.1 wt% lignin in
aqueous solution [16].
The resulting aqueous mixture (stream 28, Fig. 1a) that contains
12.6 wt% PG, 15.3 wt% GP, 1.6 wt% PS and 0.4 wt% SP is first sent to
pressure filtration (S-5, Fig. 1a) to remove 55 wt% of unconverted
lignin and humins, then fed to a decanter (S-6, Fig. 1a) to remove
most of the SP and GP from the aqueous phase. Thus, a PG-rich
mixture that contains 11 wt% PS is obtained and used internally
in the process.
2.2. Process B: simultaneous processing of C5 and C6 by using GVL
solvent derived from C5 and C6
The PFD of Process B (Fig. 1b) outlines the production of GVL
from simultaneous processing of C5 and C6 by using GVL solvent
derived from C5 and C6. This process can be broken into six main
systems: biomass handling, LA production, GVL production, WWT,
heat and electricity generation, and storage. Simulation models of
major units for the two main systems (LA production and GVL
 J. Byun, J. Han / Energy 175 (2019) 546e553
production) in this process were developed by using the ASPEN
Plus Process Simulator [29]; the other systems were designed based
on simulation results in previous studies [13,27,28].
C5 and C6 are hydrolyzed and dehydrated in a catalytic reactor
(R-1, Fig. 1b) that contains 16.0 wt% shredded CS and 0.1 M SA
catalyst in a GVL-H2O (GVL/H2O mass ratio ¼ 4) solution at 443 K to
produce FF at 56% molar yield, and LA at 61% molar yield [9]. The SA
in the liquid mixture is precipitated by neutralization using
Ca(OH)2 (S-1, Fig. 1b) and the resulting GVL-rich mixture that
contains 2.7 wt% LA and 1.4 wt% FF is fed to a dual-catalyst bed
tubular reactor (R-2, Fig. 1b) that uses Pt3Sn/SiO2 and Amberlyst 70
catalysts. FF is hydrogenated over Pt3Sn/SiO2 catalyst at 373 K and
35 bar to produce furfuryl alcohol (FFA) at 90% molar yield, and the
produced FFA is hydrolyzed over Amberlyst 70 catalyst at 398 K and
35 bar to produce LA at 70% molar yield in a H2-rich environment
(R-3, Fig. 1b) [9]. The reaction produces a liquid that contains 69 wt
% GVL, 18 wt% H2O, 5 wt% humins, 4 wt% LA, 3 wt% lignin, and 1 wt%
FA.
LA in the GVL-rich mixture is hydrogenated over RuSn(1:4)/C
catalyst in a packed bed tubular reactor (R-4, Fig. 1b) containing
5.0 wt% LA in GVL-H2O (GVL/H2O mass ratio ¼ 4) solution at 493 K
and 35 bar to produce GVL at a 99% molar yield. In the hydroge-
nation of LA, the requirements for H2 are minimized by using H2
produced internally during decomposition of FA. The resulting GVL-
rich mixture contains 19 wt% H2O, 5 wt% humins, 3 wt% lignin, and
1 wt% CO2, and is sent to three expansion tanks (S-2, Fig. 1b) in
series to remove 99% of the CO2 at the top of tanks. The CO2-free
stream is then sent to an evaporation tank (S-3, Fig. 1b) to recovery
99% of the GVL and 99.9% of the H2O as a vapor stream from a wet
solid stream that contains 55 wt% humins, 33 wt% lignin, and 12 wt
% GVL. The wet solid stream is sent to pressure filtration (S-4,
Fig. 1b) with addition of H2O (H2O/feed mass ratio ¼ 1.16) to recover
insoluble products that contain 55 wt% lignin and humins; these
products are burned in the heat- and electricity-generation system.
The aqueous stream that contains 21 wt% GVL is sent to a 16-stage
distillation column (D-1, Fig. 1b) to separate and recycle H2O to S-4
and GVL to R-1. Following evaporation of GVL with some H2O, 96%
of the vapor stream is recycled to R-1 and the remaining GVL is sent
to a 10-stage distillation column (D-2, Fig. 1b). GVL is obtained at
the bottom of D-2 at 477 K and 1 bar and sent to product storage
(stream 18, Fig. 1b); the top liquid stream of D-2 mainly consists of
H2O and is sent to the WWT system.
3. Results and discussion
In section 3.1, the ASPEN Plus Process Simulator [29] is used to
conduct an overall input-output analysis based on the assembled
process and experimental data to describe mass and energy bal-
ances. Overall energy balance was optimized by using the ASPEN
Plus Energy Analyzer [31] with the design of a heat exchanger
network (HEN). In section 3.2, the economic viability of the pro-
posed processes was analyzed by using the conceptual process
design approach that has been used in previous studies [13,27,28].
Annualized capital cost (ACC) and operating cost (AOC) were
calculated by using ASPEN Plus Economic Analyzer [30] based on
sizing (or requirements) and costing of equipment units, raw ma-
terials and utilities for each system in the process. Then, the min-
imum selling price of GVL to obtain a zero net present value of the
project lifetime for 30 years was calculated by using a discounted
cash flow analysis [23]. In section 3.3, several recommendations to
further reduce costs of the process were obtained by a sensitivity
analysis.
549
3.1. Overall input-output analysis
The main systems of the two processes produce GVL and elec-
tricity by processing 2000 t/d of corn stover. Fig. 2 shows the overall
input and output balances of the two processes. Apart from the
feedstock, the main inputs are H2, SA, and Ca(OH)2; GVL and PG are
obtained on-site. Requirements for SA (157 t/d) and Ca(OH)2 (57 t/
d) for Process A are larger than for Process B (20 t/d, 15 t/d), whereas
H2 requirements for Process B (6 t/d) are larger than for Process A
(2 t/d).
SA is used as a homogeneous catalyst to convert C6 and C5
contents of LB, and Ca(OH)2 is used to separate SA by neutralization
and precipitation. Process A sequentially converts C5 and C6 to
xylose and LA by pretreatment and LA production, which require a
large amount of SA (157 t/d). Process B simultaneously converts C6
and C5 to LA and FF by producing LA that requires a small amount of
SA (20 t/d). Input of Ca(OH)2 used for separation of SA is higher for
Process A (57 t/d) than for Process B (15 t/d).
H2 requirement for hydrogenation of LB derivatives are lower in
Process A that utilizes only C6 content than Process B that utilizes C6
and C5 contents. In Process A, xylose derived from the C5 content of
LB in H2O at low concentration is sent to WWT. This process leads
to a major difference of LB derivatives that require H2 for hydro-
genation, and to a difference in the GVL production in processes A
(98 t/d) and B (375 t/d).
Lignin and humins from Process A (1390 t/d) and B (1741 t/d) are
burned to provide the heat required for each process, and excess
energy is converted to electricity. Process A produces 71 MW (MW)
of heat and 21 MW of electricity, and Process B produces 87 MW of
heat and 23 MW of electricity.
Both processes require three type of energy (heating, cooling,
and electricity), and details are in Table 2. Heating requirements for
each process are 137 MW (Process A) and 186 MW (Process B), and
these are required to recover GVL with high purity. Through heat
integration, 66 MW (Proces A) and 99 MW (Process B) of heat are
recovered from waste heat, and the heating requirements for each
process are reduced to 52% (71 MW, Process A) and 47% (87 MW,
Process B) of their initial value. After heat integration, the cooling
requirements for each process are also reduced to 13% (10MW,
Process A) and 49% (97 MW, Process B) of their initial value.
Although the heating and cooling requirements for Process B is
significantly larger than that for Process A, the electricity re-
quirements show a different tendency. The result due to the elec-
tricity requirements for pretreatment in Process A.
Energy efficiency is calculated based on energy input (CS and
H2) and energy output (GVL and electricity). Energy inputs of Pro-
cess A (362 MW) and Process B (366 MW) are similar, and GVL
production is a major factor in determining the energy efficiency.
The energy efficiency of Process B (37%) is about three times larger
than that of Process B (13%). Compared to Process A, the effective
utilization of C5 of LB in Process B led to this result. Although xylose
liquor is sold as a byproduct in Process A, the energy content of
xylose (87.2 MW-equivalent (MWe)) is excluded in this calculation.
The concentration process for dilute xylose requiring additional
heat energy is not included in the integrated process. To clearly
compare the energy efficiency of two processes, we did not
consider the energy content of xylose and heating requirements for
xylose concentration.
3.2. Cost and revenue analysis
Annualized costs and revenues were calculated for both pro-
cesses, and they were shown in Table 3. Total cost (TC) consists of
ACC and AOC. TC is US$ 123.8 million/y for Process A, and US$ 128.1
million/y for Process B. Although the TCs of two processes are
550 J. Byun, J. Han / Energy 175 (2019) 546e553

Fig. 2. Overall input and output analysis for the two processes.

Table 2 pretreatment (US$ 9.0 million/y; 7% of TC). The major ACCs of

Energy requirements and efficiency for each process. Process B are heat and electricity generation (US$ 13.0 million/y;
(MW) Process A Process B 10% of TC), and LA production (US$ 10.9 million/y; 9% of TC). The
Beforea Afterb Beforea Afterb
ACC of three main systems (GVL production, heat and power gen-
eration, and storage) is smaller in Process A (US$ 13.4 million/y)
Heating 136.8 71.1 185.8 86.6
than in Process B (US$ 19.1 million/y) which utilizes more LB con-
Cooling 75.5 9.8 195.7 96.6
Electricity 2.2 2.2 1.1 1.1 tent than Process A. However, the ACC of four main systems (pre-
treatment, LA production, PG production, WWT) differ significantly
Process A Process B
Energy input (MWe)c 361.8 366.1 between Process A (US$ 27.4 million/y) and B (US$ 11.3 million/y), it
Energy output (MWe)c 48`.2 136.5 leads that the total ACC is higher for Process A than for Process B. In
Energy efficiencyc (%) 13.3 37.3 particular, the differences in pretreatment and LA production are
*Excluding energy contents of xylose and energy requirements for xylose noteworthy. Pretreatment used to separate C6 content in Process A
concentration. entails a high capital cost by itself but also increases the cost of
a
Before heat integration. WWT by discharging a large amount of wastewater. Although
b
After heat integration.
c Process A converts C6 content to LA excluding C5 content, LA pro-
After heat integration and on-site heat/power generation.
duction entails high capital costs for reactors due to the long re-
action time. ACC of LA production reactor in Process A (US$ 13.6
similar, their ratios of ACC and AOC differ significantly. ACC/TC of million/y) is nearly three times higher than in Process B (US$ 4.6
Process A (34%) is 10% points higher than that of Process B (24%), million/y). As a result, the ACC of LA production is higher in Process
and total ACC of Process A (US$ 41.4 million/y) is 33% higher than A than in Process B, unlike the two main systems (GVL production
the ACC of Process B (US$ 31.1 million/y). The major ACCs of Process and storage) that are heavily affected by production of LA.
A are LA production (US$ 14.4 million/y; 12% of TC), heat and The AOC/TC ratio in Process B (76%) is 10% points higher than in
electricity generation (US$ 11.4 million/y; 9% of TC), and Process A (66%). Total AOC is higher in Process B (US$ 97.0 million/
 J. Byun, J. Han / Energy 175 (2019) 546e553 551

Table 3 income (US$ 32.3 million/y, Process A) is calculated based on liquor

Cost (US$ million/y) and revenue (US$ million/y) for the two processes. price considering cost of concentrating process and the amount of
Process Block Process A Process B xylose. Electricity income is calculated based from electricity
% of TC % of TC
output and electricity price. Electricity income is higher for Process
B (US$ 12.7 million/y) than for process A (US$ 10.4 million/y). Net
Pretreatment 9.0 7.3 e e
manufacturing cost (MC) is difference between TC and income of
LA production 14.4 11.6 10.9 8.5 byproducts (xylose and electricity). Although the MC for Process B
GVL production 1.8 1.5 5.7 4.4 (US$ 115.4 million/y) is 42% higher than that for Process A (US$ 81.1
PG production 0.4 0.3 e e
million/y), MSP of GVL for Process B is 63% lower than that for
Process A. This result is due to significant difference in GVL pro-
Heat and electricity generation 11.4 9.2 13.0 10.1
duction between two processes.
WWT 3.6 2.9 0.4 0.3

Storage 0.2 0.2 0.4 0.3

3.3. Sensitivity analysis
HEN 0.6 0.5 0.7 0.5

Total capital cost 41.4 33.5 31.1 24.3 Cost analysis shows the configuration of cost in each process.
List of operating costs ACC/TC is higher in Process A than in Process B, whereas AOC/TC is
Feedstock 59.4 48.0 59.4 46.4
higher in Process B than in Process A. The three parameters (in-
ternal rate of return (IRR), catalyst lifetime, H2 price) that can cause
H2 1.8 1.5 4.2 3.3
the significant difference in ACC and AOC between the both pro-
SA 2.6 2.1 0.3 0.2 cesses are determined by considering cost analysis. The first
Ca(OH)2 2.6 2.1 0.7 0.5 sensitivity analysis is performed to observe their effect on the cost
Catalyst regeneration 0.3 0.2 20.7 16.2
of each process, and it was shown in Table 4.
The IRR is the discount rate that sets the net present value of an
Other variable operating costsa 5.0 4.0 1.9 1.5
investment equal to zero. IRR is used to quantify the attractiveness
Cooling water 0.8 0.6 1.6 1.2 of an investment; 10% was set as the default in this study. When the
Fixed operating costs 9.9 8.0 8.2 6.4 IRR is changed by ±50%, the MSP changed by ± 17% in Process A
Total operating cost 82.4 66.5 97.0 75.7
changed and by ±10% in Process B. Catalyst lifetime effect on the
catalyst regeneration cost accounts for the second-largest portion
Total cost (TC) 123.8 128.1
of the TC of Process B. In this study, 700 h was set as the default, this
Revenue is shorter than an industrial scale operation (2100 h) because im-
GVL income 81.1 65.5 115.4 90.1 purities derived from LB may affect the catalyst, but this effect has
Xylose income 32.3 26.1 e e not been quantified. The change of catalyst lifetime had little effect
Electricity income 10.4 8.4 12.7 9.9 on the MSP for Process A, but causes significant change of MSP for
Total income 123.8 128.1
Process B. When the catalyst lifetime was decreased by 50%, MSP
a
H2O, WWT chemicals, and waste disposal. for Process B increased by 18%, and when the catalyst lifetime was
increased by 50%, the MSP for Process B decreased by 6%. These
changes occur because the use of the homogeneous catalyst (SA) is
y) than in Process A (US$ 82.4 million/y). The feedstock cost (US$
more significant than the use of heterogeneous catalysts in Process
59.4 million/y) is the largest portion of TC (46e48%) in both pro-
A. H2 is used for conversion of LB derivatives to GVL, and US$ 2.1/kg
cesses. The AOC of SA, Ca(OH)2, and other variable operating costs
is set as default H2 price in this study, but the price had little effect
(H2O, WWT chemicals, disposal) is higher in Process A (US$ 10.2
on MSP. When the H2 price was changed by ± 50%, MSP changed by
million/y) than in Process B (US$ 2.9 million/y) due to sequential
± 1% in Process A and ±2% in Process B, because the share of H2 cost
conversion of C5 and C6, but the AOC of H2 and catalyst regeneration
in TC is relatively small.
is significantly higher in Process B (US$ 24.9 million/y) than in
We also consider positive and negative scenarios for each pro-
Process A (US$ 2.1 million/y). Compared with Process A, Process B
cess. In the positive scenario, the MSPs are decreased by 18% (to US$
requires a large amount of precious metal catalysts and H2 to
1.93/kg) for Process A and by 17% (to US$ 0.73/kg) for Process B. In
produce GVL, so total AOC is higher in Process B than in Process A.
the negative scenario, the MSP were increased by 19% (to US$ 2.81/
Total revenue (TR) is obtained by selling GVL, xylose, and elec-
kg) for Process A and by 30% (to US$ 1.14/kg) for Process B. This
tricity. GVL income is calculated from GVL production and MSP to
result shows that changing any of the three parameters does not
equalize TC and TR. MSP of GVL for was US$ 2.36/kg for Process A
reverse the difference in MSPs between the processes. Even if the
and US$ 0.88/kg for Process B. MSP for Process A is in the range of
positive scenario of Process A and the negative scenario of Process B
GVL market price (US$ 1.25e3.88/kg), whereas MSP for Process B is
are compared, the MSP for Process A is 69% larger than that for
lower than the range. In the Process A, xylose obtained after pre-
Process B. The difference is a result of the low productivity of
treatment is sold as liquor containing 40 wt% of xylose. Xylose
Process A. To improve the process economics and overcome

Table 4
Effects of economic parameters on the MSP.

Unit: US$/kg Internal Rate of Return (IRR) Catalyst lifetime H2 price

5% (50%) 10% (base) 15% (þ50%) 350 h (50%) 700 h (base) 1050 h (þ50%) US$ 1.1/kg (50%) US$ 2.1/kg (base) US$ 3.2/kg (þ50%)

Process A 1.96 2.36 2.78 2.37 2.36 2.36 2.34 2.36 2.39
Process B 0.80 0.88 0.96 1.04 0.88 0.83 0.86 0.88 0.89

- Positive scenario: US$ 1.93/kg (Process A), US$ 0.73/kg (Process B).
- Negative scenario: US$ 2.81/kg (Process A), US$ 1.14/kg (Process B).
552 J. Byun, J. Han / Energy 175 (2019) 546e553
Fig. 3. MSP of GVL for Process A producing chemicals from C5.
economic bottlenecks in the Process A, increase of GVL production
by utilization of C5 content is required.
We additionally identified the effect of utilization of C5 on
process economics of Process A. FF and its derivatives are repre-
sentative chemicals which can be produced from C5, and various
studies on their economic potential have been reported [31]. We
determined the MSP of GVL when xylose is converted to FF or FF
derivatives (FFA and maleic anhydride (MA)), and the result is
shown in Fig. 3. In the second sensitivity analysis, revenue of each
chemical was calculated based on possible theoretical yield
(57e78 mol%) and current market price (US$ 0.76e1.6/kg).
Although the production of byproducts decreased in alternative
cases requiring additional conversion process, the revenue of
byproducts increased compared to the base case selling xylose li-
quor. It led to a significant decrease (39e85%) in MSP of GVL in
alternative cases. In the two cases producing FF (US$ 1.43/kg) or FFA
(US$ 1.34/kg), the MSPs were close to the MSP range of Process B
(US$ 0.73e1.14/kg). Especially, the MSP for Process A producing MA
(US$ 0.36/kg) is 59% lower than that for Process B (US$ 0.88/kg). In
this analysis, the processing cost for additional conversion and
separation processes was not considered. If the processing cost of
the alternative case producing MA is less than US$ 17.7 million/y,
the overall process economics of Process A and B will be reversed.
4. Conclusions
To evaluate the economics of two processes (single processing of
C6 by using lignin-derived PG solvent (Process A) and simultaneous
processing of C5 and C6 by using GVL solvent derived from C5 and C6
(Process B)) to produce GVL from LB, large-scale processes handling
2000 t/d of corn stover were assembled based on experimental
data. GVL production in Process B (375 t/d) is 2.8 times larger than
in Process A (98 t/d), due to efficient utilization of the C5 in LB
content in Process B. The energy requirements for the two pro-
cesses are satisfied by burning biomass residues (lignin and
humins), and the excess electricity is sold off-site. The energy ef-
ficiencies calculated based on energy input and output are 13.3%
(Process A) and 37.3% (Process B). Economic analysis shows that the
MSP for Process A (US$ 2.36/kg) is in the current market price
range, whereas that of Process B (US$ 0.88/kg) is much lower than
the range. The difference in MSP is a result of low GVL production in
Process A, although the TCs of the two processes are similar. The
sensitivity analysis showed that producing FF or FF derivatives (FFA
and MA) from C5 had the larger impact on the process economics
than varying the key parameters (IRR, catalyst lifetime, and H2
price). When the Process A converts xylose to MA, the MSP for
Process A (US$ 0.36/kg) could be 59% lower than that for Process B
(US$ 0.88/kg). These results show that effective utilization of
hemicellulose in LB content is significant to improve process eco-
nomics. Development of novel technology that simultaneously
utilize the major components in LB will facilitate commercialization
of biorefinery system.
Author contributions
All authors have given approval to the final version of the
manuscript.
Acknowledgements
This research was supported by Basic Science Research Program
through the National Research Foundation of Korea (NRF) funded
by the Ministry of Education (2016R1D1A3B03934107) and NRF
(National Research Foundation of Korea) Grant funded by the
Korean Government (NRF-2018-Global Ph.D. Fellowship Program).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.energy.2019.03.070.
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