catalysts

Article
Implementation of Formic Acid as a Liquid Organic Hydrogen
Carrier (LOHC): Techno-Economic Analysis and Life Cycle
Assessment of Formic Acid Produced via CO2 Utilization
Changsoo Kim 1 , Younggeun Lee 2 , Kyeongsu Kim 1, * and Ung Lee 1,3,4, *

1 Clean Energy Research Center, Korea Institute of Science and Technology, Seoul 02792, Korea
2 System Research Center, Yullin Technologies Co., Ltd., Seoul 06245, Korea
3 Division of Energy and Environmental Technology, KIST School, Korea University of
Science and Technology (UST), Seoul 02792, Korea
4 Green School, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul 02841, Korea
* Correspondence: [email protected] (K.K.); [email protected] (U.L.)

Abstract: To meet the global climate goals agreed upon regarding the Paris Agreement, governments
and institutions around the world are investigating various technologies to reduce carbon emissions
and achieve a net-negative energy system. To this end, integrated solutions that incorporate carbon
utilization processes, as well as promote the transition of the fossil fuel-based energy system to
carbon-free systems, such as the hydrogen economy, are required. One of the possible pathways
is to utilize CO2 as the base chemical for producing a liquid organic hydrogen carrier (LOHC),
using CO2 as a mediating chemical for delivering H2 to the site of usage since gaseous and liquid
H2 retain transportation and storage problems. Formic acid is a probable candidate considering
its high volumetric H2 capacity and low toxicity. While previous studies have shown that formic
Citation: Kim, C.; Lee, Y.; Kim, K.; acid is less competitive as an LOHC candidate compared to other chemicals, such as methanol or
Lee, U. Implementation of Formic
toluene, the results were based on out-of-date process schemes. Recently, advances have been made
Acid as a Liquid Organic Hydrogen
in the formic acid production and dehydrogenation processes, and an analysis regarding the recent
Carrier (LOHC): Techno-Economic
process configurations could deem formic acid as a feasible option for LOHC. In this study, the
Analysis and Life Cycle Assessment
potential for using formic acid as an LOHC is evaluated, with respect to the state-of-the-art formic
of Formic Acid Produced via CO2
Utilization. Catalysts 2022, 12, 1113.
acid production schemes, including the use of heterogeneous catalysts during thermocatalytic and
https://doi.org/10.3390/ electrochemical formic acid production from CO2 . Assuming a hydrogen distribution system using
catal12101113 formic acid as the LOHC, each of the production, transportation, dehydrogenation, and CO2 recycle
sections are separately modeled and evaluated by means of techno-economic analysis (TEA) and life
Academic Editor: Ioannis V.
cycle assessment (LCA). Realistic scenarios for hydrogen distribution are established considering
Yentekakis
the different transportation and CO2 recovery options; then, the separate scenarios are compared to
Received: 30 August 2022 the results of a liquefied hydrogen distribution scenario. TEA results showed that, while the LOHC
Accepted: 20 September 2022 system incorporating the thermocatalytic CO2 hydrogenation to formic acid is more expensive than
Published: 26 September 2022
liquefied H2 distribution, the electrochemical CO2 reduction to formic acid system reduces the H2
Publisher’s Note: MDPI stays neutral distribution cost by 12%. Breakdown of the cost compositions revealed that reduction of steam usage
with regard to jurisdictional claims in for thermocatalytic processes in the future can make the LOHC system based on thermocatalytic CO2
published maps and institutional affil- hydrogenation to formic acid to be competitive with liquefied H2 distribution if the production cost
iations. could be reduced by 23% and 32%, according to the dehydrogenation mode selected. Using formic
acid as a LOHC was shown to be less competitive compared to liquefied H2 delivery in terms of LCA,
but producing formic acid via electrochemical CO2 reduction was shown to retain the lowest global
warming potential among the considered options.
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
Keywords: hydrogen economy; formic acid; liquid organic hydrogen carrier; techno-economic
This article is an open access article
distributed under the terms and
analysis; life-cycle assessment
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).

Catalysts 2022, 12, 1113. https://doi.org/10.3390/catal12101113 https://www.mdpi.com/journal/catalysts

Catalysts 2022, 12, 1113 2 of 21

1. Introduction
Climate change is a global issue, and various institutions and governments around
the world are working together to find a viable solution to the crisis. To promote the
participation of countries around the globe, the Paris Agreement was held by the United
Nations Framework Convention on Climate Change (UNFCCC) in 2015 [1]. According to
the agreement, participating countries have to devise strategies for mitigating greenhouse
gases to maintain the temperature increase to below 2.0 °C, with respect to preindustrial
levels. A technical report published later on by the Intergovernmental Panel on Climate
Change states the consequences of temperature rise of 1.5 °C compared to preindustrial
levels, and thus governmental policies and protocols are being enacted to find methods for
effectively achieving this goal. Given the complexity of the objective, various methods are
being investigated to reduce greenhouse gas emissions and renovate the economy to be
less dependent on fossil fuels.
Carbon capture, utilization, and storage (CCUS) is deemed one of the most probable
short-to-mid-term solutions for mitigating carbon emissions. The idea is to capture CO2
from emission sources, such as flue gas, then purify it for utilization as a raw material for
sequential chemical production, or store it underground for permanent fixation. While
the overall concept is clear, and various research efforts have been made to find a viable
pathway, many hurdles still need to be overcome for the large-scale application of these
technologies. The biggest concern related to the implementation of the different CCUS
technologies is the economical feasibility. CO2 contains carbon, which means that with
an effective pathway, it can be converted into many forms of valuable material. However,
since CO2 itself is a very stable chemical, most pathways require an excessive amount of
energy input to accelerate the conversion process [2]. Thus, many research groups are
working on the development of appropriate catalysts in coordination with process systems
development to acquire profitable pathways applicable on a commercial scale [3].
One of the promising candidates for CCU-based chemical production is formic acid
(FA) [4]. Previous studies have shown the large potential for CO2 mitigation when incor-
porating CCU-based FA production [5–7]. However, CCU-based FA production suffers
from the limitations of low profitability due to large amounts of energy required and small
market availability. CCU-based FA production is mainly studied based on two processes,
namely the thermocatalytic hydrogenation of CO2 to FA (tcFA), and the production of
formate via electrochemical CO2 reduction (ecFA). After the initial conceptualization by
BP Chemicals [8,9] and BASF [10,11], the tcFA production process has been studied and
developed with the goal of commercialization. Pérez-Fortes et al. [12] presented the techno-
economic, environmental evaluation, and market potential of tcFA production. The results
of the study showed that, while a net amount of CO2 consumption is possible with the
integration of renewable electricity for the electrolyzers and steam generators, the overall
process is not economically competitive with the conventional FA production process,
mainly due to the use of a homogeneous catalyst and large amounts of steam usage within
distillation columns. A recent study by Kim and Han [13] provided promising results
for tcFA production incorporating the AuTiO2 catalyst, which is a heterogeneous catalyst
developed by Preti et al. [14]. The proposed catalyst showed high CO2 conversion of 84%
under 180 bar and 40 °C, with minimal production of side products (0.5 mol% of CO). While
the high conversion of 84% and heterogeneous property of the catalyst allowed profitability
as well as sustainability of the tcFA process, the performance of the catalyst was only tested in
batch conditions and cannot represent the actual tcFA performance of a continuous process.
Production of FA via the ecFA pathway is another intensely studied field [15]. The tech-
nology of producing formate from CO2 reduction has shown good progress over recent
years, and ecFA production is deemed to retain a technology readiness level (TRL) of 4–6 [4].
However, the key hurdle for commercializing FA production via ecFA lies in the fact that the
product concentration has to be increased, and that the produced formate has to be further
distilled from other electrolytes to obtain purified FA [16]. The previous studies regarding
the tcFA and ecFA pathways show that, while technological improvements are being made,
Catalysts 2022, 12, 1113 3 of 21

practical hurdles need to be overcome to enhance the profitability of the pathways, and that
an additional market for increasing the demand for CCU-based FA is required.
Apart from studying CCU as the short-to-mid-term solution for tackling climate
change, research efforts to fundamentally reduce fossil fuel usage have been made in recent
years. A highly noted option is the use of H2 as the main source of energy, a core idea of
constructing the alleged “hydrogen economy” [17]. While using H2 as the main source of
energy may seem to be an ideal solution to solve climate issues, regarding the large heat
of combustion per unit mass (141.8 MJ/kg), the possibility of carbon-free production via
electrolysis of water using renewable electricity, and the clean byproducts upon combustion
free of NOx, SOx, and CO2 , the main issues that need to be dealt with are the transportation
and storage problems. H2 has a boiling point of −253 °C, which means that it has to be
either compressed to high pressures of 200–500 bar for gas-phase transport or refrigerated
to −253 °C for liquid-phase transport. The compression and liquefaction processes require
an extensive amount of energy, and are prone to operational problems such as boil-off
gas generation, and system safety [18]. To overcome these limitations, liquid hydrogen
organic carriers (LOHCs), which are organic chemicals existing as a liquid phase in ambient
conditions, are being considered as alternative options for H2 distribution. An LOHC
consists of a base chemical, which can be hydrogenated, delivered to usage sites in ambient
conditions, dehydrogenated to supply H2 , then returned to the original site of production
to be reused as a carrier. An ideal LOHC can efficiently supply H2 to the site of usage,
relieving the burden of high-pressure or low-temperature operation when dealing directly
with H2 . Among the several options of LOHCs considered, FA is a highly probable option
for H2 distribution, owing to its high volumetric H2 capacity and relatively low toxicity
and flammability [19]. While few studies have studied the potential of using FA as an
LOHC [20–22], and presented FA to be less competitive as a LOHC compared to other
chemicals such as toluene or methanol, these studies are limited in that they do not fully
consider the techno-economic and environmental potential of the full LOHC cycle in
detail, where the base chemical is returned to its original site of production. Furthermore,
the economic and environmental results need updates and have to take in the progress
of catalysts and process configuration development provided by recent studies. Both for
tcFA and ecFA pathways, the process systems considered in the LOHC studies are based
on unprofitable configurations, which can greatly underestimate the potential of using FA
as an LOHC. Considering the fact that FA is a highly probable CCU application, which has
been gaining attention in recent years, the implementation of FA as an LOHC could allow
synergistic effects for CCU and hydrogen distribution, where the overall CCU market is
expanded and the H2 distribution network promoted.
In this study, the potential for using FA as an LOHC (the FA-LOHC system) to pro-
mote the hydrogen economy was comprehensively analyzed regarding state-of-the-art FA
production technologies and realistic scenarios. CO2 hydrogenation-based FA production
has high potential for implementation as an LOHC, due to the integration of CO2 utilization
and H2 distribution. Unlike previously studied LOHCs, FA is capable of permanently
fixing CO2 from the atmosphere, which can further contribute to the CO2 mitigation while
serving as an efficient H2 distribution vector. For extensive analysis, recently developed
tcFA and ecFA pathways are combined with two different CO2 recovery pathways to be
reused as the base chemical. Each section of the FA-LOHC system, namely the production
of FA, transportation, dehydrogenation of FA and CO2 recovery, H2 compression, and
return of CO2 , is modeled using a process simulation software Aspen Plus, then the sep-
arate models are integrated into various scenarios to conduct techno-economic analysis
(TEA) and life cycle assessment (LCA). The results are compared with liquid H2 transport,
and the technical improvements that are required to improve the FA-LOHC system are
identified. The following sections of this study are organized as follows: The results of the
TEA, sensitivity analysis, and LCA are analyzed and compared in Section 2. In Section 3,
the FA-LOHC system is defined, and the related process models are explained in detail.
In Section 4, information on the methodologies implemented throughout the study, includ-
Catalysts 2022, 12, 1113 4 of 21

ing TEA and LCA, is provided, and specific assumptions and incorporated parameters are
reviewed. The conclusions of the study are presented in Section 5.

2. Results and Discussion

2.1. TEA Results
As the base case analysis, an FA production plant producing 100 kt/y is considered,
which corresponds to approximately 12 t/d H2 production. The hydrogen refueling station
(HRS) sites are assumed to be located 400 km away from the production site, and at
each site, the HRS has a capacity of 850 kg/d. For the base-case parameters regarding
the values provided in Table 1, the economic potential of the four different scenarios
presented in Table 2, are provided in Figure 1. Compared to scenario 1, where liquefied H2
is distributed, scenario 3 shows better profitability, whereas scenarios 2 and 4 show higher
costs. Scenario 3, which incorporates the ecFA production and LCO2 transportation, retains
the lowest levelized cost of hydrogen (LCOH) value of 23.16 $/kgH2 , which is 12% smaller
compared to scenario 1. Comparing scenarios 2 and 4, the low cost of scenario 2 is attributed
to the low production and transportation costs of FA. The tcFA process uses extensive
amounts of steam, resulting in high operating costs and, consequently, high production
costs for FA. Scenario 4 retains lower dehydrogenation and compression costs compared
to scenarios 2 and 3 due to the use of an amine absorber for CO2 recovery rather than an
energy extensive pressure swing adsorption (PSA) unit. However, the transportation cost
is greatly increased since additional trailers are required for delivering the triethylamine
(TREA) required for the CO2 capture process. Since the cost of the transportation section
increases linearly with the increase of freight mass without additional advantages of the
economy of scale, it serves as a bigger disadvantage compared to other scenarios.

Table 1. Base parameters used for TEA of processes.

Parameter Name Unit Value

Process life span Year 15
Operation time h · y−1 8000
Construction period Year 2
Interest rate % 15
Income tax rate % 38.92
MACRS – 7-year class
Reference year – 2020
CEPCI (2020) – 596.2
H2 distribution capacity t/d 12
Transportation distance km 400
Capacity of HRS kg/d 850

The cost compositions of the LCOHs with regard to the components of the operational
expenditure (OPEX), including electricity, refrigeration, steam, and transportation fuel,
are presented in Figure 2. Since OPEX shows larger contributions to cost compared to
capital expenditure (CAPEX), analysis of the OPEX compositions can provide insight into
the sections that need improvement for further cost reduction. For all of the scenarios,
fuel usage for the transportation process is the largest cost factor that cannot be easily
reduced. For scenarios 2–4, the FA production process retains the largest costs, where steam
usage is dominant for tcFA, and electricity usage is dominant for ecFA. The tcFA process
requires excessive amounts of steam to operate the three distillation columns, especially
when evaporating water and TREA. Thus, to reduce costs regarding scenarios 2 and 4,
reduction of steam usage via energy optimization or discovering new amines with higher
solubility to water is required. It can be deduced from Figures 1 and 2 that scenarios 2
and 4 may become competitive with scenario 1 if production costs could be lowered by
23% and 32%, respectively. The ecFA process requires large amounts of electricity for
operating the electrolyzer. Thus, future developments of catalysts or system configurations,
 Figure 4. TEA analysis
Catalysts 2022, 12, 1113 5 of 21

which can enhance the FE or reduce the working potential, should be the focus of research.
Furthermore, the supply of cheap electricity in the future may allow further cost reduction
for scenario 3.
40
Dehydrogenation Production Compression
Fuel
Transportation Storage Liquefaction 42%
42%
Levelized Cost of Hydrogen
30
4.
(2020$/kgH2)

Electricity
20 4.7%

S
Ele
3.8
10 Electricity
9.6%

0 1
Scenario 1 Scenario 2 Scenario 3 Scenario 4
nalysis
TEA analysis Figure 1. LCOH of the four scenarios and breakdown of the costs into each section of the process.
TEA analysis 51.

. TEA analysis (a) (b)

Liquefaction Electricity Electricity Production Fuel
Electricity Electricity Production
Transportation
Transportation 51.3%
Liquefaction Electricity 3.3%
Compression
Compression Electricity 3.3% 4.8% 4.8% Dehydrogenation
Storage 8.4% 8.4% Dehydrogenation
Storage Compression
Transportation Electricity Electricity Compression
Production
Transportation
Liquefaction
Electricity 3.3% 4.8% Transportation
Compression
S
8.4% Electricity Electricity Production Dehydrogenation
Storage
Liquefaction
Electricity 3.3% 4.8% Compression
Transportation
Transportation
Compression
Dehydrogenation
Storage 8.4%
ction CompressionCompression
Production Transportation 3.4% 3.4% Compression
Fuel Fuel 8.7% 8.7%
ge LiquefactionLiquefaction
Storage 42% 42% Steam
Steam
Production Compression 42% 42% 43.1%43.1%
3.4% 36.8%
36.8%
Fuel 53.3% 53.3% 8.7%
Storage Liquefaction ElectricityElectricity
on Production Compression 42% 3.4% Steam
Fuel 53.3% 53.3% 8.7%
Storage Liquefaction 42% 42% 43.1% 36.8%
44.8% 44.8% Steam
53.3%
4.7% 42%4.7% Electricity 43.1% 36.8%
53.3% 53.3%
Electricity
53.3%
4.7% Fuel Fuel 44.8%
4.7% 44.8% 44.8% 44.8%
Electricity Electricity Refrigeration
4.7% Fuel Refrigeration
4.7% 1.6%

Scenario
Electricity Scenario
1 1 Fuel 44.8%
44.8%
Scenario
Scenario 2 2
1.6%

Electricity Refrigeration
4.7% Refrigeration
4.7% 1.6%
Electricity Scenario 1 Production Scenario
Scenario
2
1.6%
Electricity
24.1%
Production
Electricity 3.8%
Electricity
Scenario
(c)1 ProductionTransportation Electricity Production
Transportation
3.8% Transportation
Dehydrogenation 4.1%
(d) Transportation
Dehydrogenation
Electricity 9.6%
Dehydrogenation
Compression Dehydrogenation
Compression
9.6% Electricity Production Electricity Production
Electricity Compression
Production Electricity Compression
Production
3.8% Transportation 4.1% Transportation
Electricity 3.8% Transportation 4.1% Transportation
Electricity Electricity
Dehydrogenation Dehydrogenation
9.6% Dehydrogenation
Electricity Dehydrogenation
9.6% 34.7%
Compression
Compression Compression
Compression
34.7% Steam
3.9%
10% Electricity 31.7%
Steam
3.9% Electricity
ario 2 Scenario 3 Scenario 4 10% 34.8% 34.7%34.7% 31.7%
cenario 3 Scenario 4 34.8% Steam Steam
3.9%
3.9%
10%10% 31.7% 31.7%
ario
nario2 2 Scenario
Scenario33 Scenario
Scenario 4 34.8%
34.8%
62.7%
51.3% Fuel 62.7%
Fuel 62.7%
51.3%
62.7% 62.7% 62.7%
Fuel 51.3%
51.3% Fuel Fuel 0%

51.3% 62.7% 62.7%

Fuel 0% Refrigeration
51.3% 1.4%
Fuel
Fuel 0%
0% Refrigeration
51.3%
51.3%
Scenario 3 Scenario 4 1.4%
Refrigeration
1.4%
Refrigeration

Scenario 3 Scenario 4 1.4%

Scenario 3 3 Scenario 4
Scenario 4
Scenario

Figure 2. OPEX broken-down into utilities used in specific sections. (a–d) correspond to the OPEX
evaluation results of scenarios 1–4 listed in Table 2, where the relative contribution of each cost factor
is shown. Individual legends are used for the figures.
Catalysts 2022, 12, 1113 6 of 21

Table 2. Details of the analyzed H2 supply scenarios.

FA
Scenario Name FA Production FA Transportation CO2 Return
Dehydrogenation
Scenario 1 Liquid H2 Green H2 LH2 Direct use Not required
Thermocatalytic + Green H2 , LCO2 , Dehydrogenation +
Scenario 2 FA LCO2
LCO2 Amines PSA
Electrochemical + Green H2 , LCO2 , Dehydrogenation +
Scenario 3 FA LCO2
LCO2 Amines PSA
Thermocatalytic + Green H2 , Dehydrogenation +
Scenario 4 FA, TEA/H2 O AmineCO2
LCO2 AmineCO2 CO2 capture

2.2. Sensitivity Analysis Results

In this section, the sensitivity analysis results for the selected parameters are presented.
The overall contribution of the different parameters are first analyzed using global sensitiv-
ity analysis (GSA), then individual parameters of interest, namely H2 production capacity
and transportation distance, are further analyzed.
Regarding GSA, the selected parameters and the boundaries of the analyzed values
are presented in Table 3. For most of the parameters, the values are varied from −20%
of the nominal value to +20%, to allow a fair basis for contribution calculation. As for
parameters such as CO2 capture rate and FE of ecFA, the minimum and maximum values
are set to a wider range to take into consideration their large uncertainties.

Table 3. Names and value ranges of the parameters subject to change during GSA.

Parameters Nominal Value Minimum Value Maximum Value

Cost of electricity ($/kWh) 0.07 0.056 0.084
CO2 capture rate (%) 90 80 100
TREA loss (%) 1 0 5
H2 production cost ($/kgH2 ) 4 3.2 4.8
FE of ecFA 0.9 0.7 1
Steam cost (ratio) 1 0.8 1.2
Cost of TREA ($/kg) 1.56 1.248 1.872
Boil-off ratio 0.06 0.048 0.072

GSA results of the eight different parameters are presented in Figure 3. The relative
contributions of the parameters to the LCOH of the four scenarios, and the differences
among scenarios can be deduced from this figure.
For scenario 1, the H2 production cost and the boil-off ratio during liquid H2 transport
are the only parameters affecting the LCOH value. Due to the low-energy consumption,
electricity cost barely induces any change in the economic performance. Since the Sobol
index values represent the relative contribution of each factor to the cost, the high correlation
of H2 production cost reflects the fact that the CAPEX and OPEX of the liquefied H2
transportation system is relatively low, and the input material cost is the dominant factor
that determines the overall cost. Smaller contributions are observed for the boil-off ratio
because the changes in these values affect the overall costs on a much smaller scale due to
the economy of scale effects and small values of boil-off ratios.
Regarding scenario 2, H2 production cost is the dominant contributor as in the case of
scenario 1, with additional contributions observed from steam cost and TREA cost, showing
Sobol index values of 0.20 and 0.17, respectively. Since the tcFA process incorporates large
amounts of steam, and some of the TREA used as input are lost during the operation of the
process, changes made in the costs of the two factors largely affect the overall cost.
Catalysts 2022, 12, 1113 7 of 21

Scenario 1
CO2 Loss Ratio Scenario 2
Scenario 3
1.0 Scenario 4

Boil-off Ratio 0.8 Electricity Cost

0.6
0.4
0.2
0.0

TREA Cost TREA Loss Ratio

Steam Cost H2 Prod. Cost

FE of ecFA
Figure 3. GSA result of the eight different parameters simultaneously analyzed within a defined
variable space.

The GSA results of scenario 3 also show that H2 production cost is the dominant
factor for economic feasibility, showing a Sobol index value of 0.62. However, unlike the
previous cases, the cost of electricity greatly affects economic performance, showing a Sobol
index value of 0.38. This is induced by the large amounts of electricity incorporated in
operating the electrolyzer, and since the electrolyzer is less affected by the economy of
scale compared to conventional process equipment, its relative contribution is amplified.
This shows potential for the ecFA process to further improve economic performance in the
future if electricity costs could be lowered due to the extended use of renewable electricity.
The LCOH of scenario 4, unlike the previous scenarios, is predominantly affected by
the amine loss ratio, which considers the loss of TREA during the CO2 process after the
dehydrogenation step. Although the absolute value of TREA loss is small, due to the expen-
sive cost of TREA and the large amounts incorporated during the tcFA production process,
the contribution to cost is large, showing a Sobol index value of 0.67. Accordingly, the TEA
cost is the next largest contributor, with a Sobol index value of 0.14, emphasizing the effect
of TREA-related costs on the overall cost. Considering the GSA results of scenarios 2 and 4,
it can be deduced that TREA management is a critical factor in the economic performance
of the tcFA process, and for further improvement, future research should be directed to the
development of amine liquefying sequences to prevent evaporation, or to find new amines
with low volatility.
For an intuitive comparison of the LCOH for the four scenarios, local sensitivity anal-
ysis results with regards to the H2 production capacity and transportation distance are
provided in Figure 4. The H2 production capacity, is varied from 10 t/d to 50 t/d, and
transportation distance is varied from 100 km to 1000 km. Regarding the H2 production
capacity, scenario 4 shows a steep increase rate with respect to the increase of the pro-
duction capacity, compared to other scenarios. This is mainly due to the larger increase
in transportation cost for scenario 4, since additional costs are required for the increased
amount of water and TREA corresponding to the increased amount of FA. Interestingly,
the relative cost difference of scenarios 1–3 is altered with respect to the increase of H2
production capacity, since the transportation costs increase in a discrete manner, according
Catalysts 2022, 12, 1113 8 of 21

to the number of trailers required. Thus scenarios 2 and 3 show a larger increase in costs
according to the increasing H2 production capacity, and the cost of scenario 3 exceeds that
Figure 6. GSA results Figure 따른
Capa에 6. GSA results Capa에 따른 변화….
of scenario 1 when H2 is produced at 30변화….
t/d. This trend is not observed for transportation
distance change, since the cost is increased continuously.

(a) (b)
70 50
Scenario 1 Scenario 1
Scenario 2 Scenario 2
60 Scenario 3 Scenario 3
Scenario 4 40 Scenario 4

Levelized Cost of Hydrogen

Levelized Cost of Hydrogen

50

(2020$/kgH2)
(2020$/kgH2)

30
40

30
20

20

10
10

0 0
10 20 30 40 50 100 200 300 400 500 600 700 800 900 1000
H2 Production Capacity (t/d) Transportation Distance (km)

Figure 4. Local sensitivity analysis showing LCOH change of the scenarios according to changes
made in (a) H2 production capacity and (b) transportation distance.

2.3. LCA Results

The LCAs of the different scenarios were conducted using the commerical software
SimaPro. The LCA results for each of the scenarios are presented in Figure 5. Since the
main components of concern during the LCA of a CCU process are the global warming
potential (GWP) and fossil resource scarcity (FRS), results for the two values are presented
only [23].
In accordance with the previous studies regarding the LCA of LOHCs compared to
H2 transportation, both the GWP and FRS values are higher when utilizing LOHCs for H2
distribution. While liquefied H2 processes require the use of refrigerants such as R134a,
refrigerants are recycled within the system for the entire process life cycle (assuming no
leakage), contributing negligibly to the environmental impact factors. However, LOHC
systems tend to require a continuous input of energy for steam or electricity generation
and thus show higher values of GWP and FRS compared to the liquefied H2 process.
For both GWP and FRS values, the liquefaction process is the largest contributor considering
scenario 1, due to large requirements of electricity for liquefaction system. This is in
accordance with the OPEX breakdown results shown in Figure 2a. Comparing scenarios
2–4, the largest difference in GWP and FRS values is attributed to the FA production
process. Due to the large amounts of steam usage in the tcFA process, scenarios 2 and 4 are
observed to emit more than two times the amount of GWP and FRS compared to scenario
3. Furthermore, scenario 4 shows higher GWP and FRS costs compared to scenarios 2
and 3 due to the larger contribution of the transportation section. Due to the additional
transportation requirements for TREA, which is to be used during the CO2 capture process,
the GWP and FRS values are increased by a factor of 3.76 compared to values for scenarios
2 and 3. From these results, while the direct hydrogenation of TREA-captured CO2 might
seem to be a better solution for FA-LOHC distribution at first glance, the additional costs
and environmental impacts induced by the large volume of additional freight drives the
scenario to show poor performance compared to liquefied CO2 transport.
Catalysts 2022, 12, 1113 9 of 21
Figure 5. LCA analysis
Figure 5. LCA analysis

(a) (b)
150 150 50 50
NH3 Compensation NH3 Compensation Liquefaction Liquefaction
Liquefaction Transportation Transportation
Liquefaction
Transportation Transportation Dehyd. LCO2 Dehyd. LCO2
120 120LCO
Dehyd. 40 40 AmineCO
Dehyd. Dehyd. AmineCO2
Dehyd. LCO2 2
Global Warming Potential

Global Warming Potential

Fossil Resource Scarcity

2

Fossil Resource Scarcity

Dehyd. AmineCODehyd. AmineCO2 Elec. FA Prod. Elec. FA Prod.
2
(kg CO2 eq./kg H2)

(kg CO2 eq./kg H2)

Thermo. FA Prod.
Thermo. FA Prod.

(kg oil eq./kg H2)

(kg oil eq./kg H2)

Elec. FA Prod. Elec. FA Prod.
90 Thermo.
90 FA Prod.Thermo. FA Prod. 30 30

60 60 20 20

30 30 10 10

0 0 0 0
Scenario 1 Scenario21
Scenario Scenario 32
Scenario Scenario 4
Scenario 3 Scenario 4 Scenario 1 Scenario
Scenario12 Scenario
Scenario2 3 Scenario
Scenario34 Scenario 4

Figure 5. The LCA results of the four scenarios, regarding (a) GWP values and (b) FRS values.

3. System Definition and Process Modeling

For a fair comparison of the various combinations of FA-LOHC distribution technolo-
gies, a systematic approach for formulating the different cases should be applied. In this
study, a hydrogen distribution cycle where mass amounts of FA are produced at a central
site, and the produced FA is transported to usage sites using tank lorries, is assumed. It is
assumed that H2 produced using renewable energy, namely “green H2 ”, is delivered from
outside sources for conversion into FA, then the produced FA is delivered to the site of
usage and distributed with regards to the required H2 purity and pressure. The delivery
of H2 to an HRS is considered in this study, where 99.99% of H2 is required at 900 bar.
The hydrogen distribution cycle can be divided into four different sections, namely the
process of FA production, transportation of FA to the HRS site, dehydrogenation of FA for
H2 extraction, and return of CO2 to the central site for re-conversion into FA. A schematic
overview of the defined FA-LOHC distribution cycle is shown in Figure 6. The overall cycle
of FA production, transportation, dehydrogenation, and CO2 recycle is presented, and the
different options available for each section of the cycle are provided within the system box.
For FA production, the tcFA and ecFA pathways, are considered. The difference of the two
pathways lies not only in the form of energy used and system configuration, but also in the
possible form of CO2 usable as an input. The tcFA process can utilize the amine-captured
CO2 state as well as pure CO2 as the process input, meaning that CO2 does not necessarily
have to be purified with the use of additional energy for operating the tcFA process. This
aspect leads to two different options for CO2 recovery and transportation, which are the
PSA and CO2 absorption, and the liquefied CO2 and amine-captured CO2 delivery, respec-
Figure 1. Overall defined scenario
tively. The ecFA process can only incorporate pure CO2 as the input, and thus only the
CO2 recovery using PSA and the liquefied CO2 transportation option can be integrated.
A summary of the considered H2 distribution scenarios are provided in Table 2.

Green H2

FA Transportation

FA Dehydrogenation
FA Production & CO2 Recovery Refuelling
H2
- Thermocatalytic - PSA station
- Electrochemical - CO2 absorption

CO2 Transportation
- Liquefied CO2
- Amine-captured CO2

Figure 6. Overview of the H2 distribution cycle using FA as an LOHC. Different options for each step
of the process are listed.
Catalysts 2022, 12, 1113 10 of 21

3.1. Process Modeling

To obtain reliable TEA and LCA results, each step of every scenario is modeled using
the commercial process simulator Aspen Plus. For each option of the process designed,
the operational parameters and performance indicators are obtained mainly from related
studies showing state-of-the-art performance. It should be noted that since the information
required for rigorous modeling of the reactors, such as packing, pressure drop, and kinetic
models, are unavailable at the current stage of development, equilibrium models are used
assuming the performances are preserved after scale-up of the process. Afterwards process
configurations are further analyzed using pinch analysis to integrate hot and cold streams
and maximize energy efficiency.

3.1.1. Thermocatalytic CO2 Hydrogenation to FA

The reaction of CO2 and H2 to produce FA is a nonspontaneous reaction, retaining a
standard Gibbs free energy change of 32.9 kJ/mol [19]. Thus, to enable this reaction, tcFA
processes incorporate the use of reaction amines and appropriate catalysts.
The tcFA process is modeled based on the process design presented in Park et al. [24].
Park et al. proposed the use of a Ru molecular catalyst supported on bpyTN-30-CTF,
to be used as a heterogeneous catalyst for CO2 hydrogenation in a trickle-bed reactor [24].
The results of the study showed that by using the Ru-based catalyst in a continuous-
flow reactor at 120 bar and 120 °C, 48% conversion of CO2 to formate was achieved,
with stable performances for over 30 days and minimal amounts of side product production
(300–600 ppm of CO, <5 ppm of CH4 ). While various studies exist for modeling the tcFA
process [13,25], the Ru-based catalyst developed by Park et al. is the only process that
has been validated with respect to a continuous process, which is an essential aspect for
obtaining realistic results. Process operating conditions and parameters required for the
process model are provided in Table S1.
As shown in the simplified tcFA process flow diagram in Figure 7a, the main units of
the tcFA process are the trickle-bed reactor, and three distillation columns. In this process,
TREA is used as the reaction amine and n-butylimidazole (nBIM) is used as the auxiliary
amine. The trickle-bed reactor is filled with Ru-based catalysts, and operates at 120 °C and
120 bar to convert bicarbonate ions into formate with a conversion value of 48%. The first
distillation column, called the evaporator, uses steam to evaporate the water and TREA
within the product of the reactor. This step is required to increase the acid-to-amine ratio of
the reactor product and to allow efficient operation of the latter columns. Water and TREA
obtained from the top product are recycled and stored in storage tanks, either to be reused
in reactors or to be transported to FA dehydrogenation sites to be used for CO2 capture.
The concentrated TREA-formate adduct obtained from the bottoms of the evaporator is
sent to the amine exchange column, where the formate is transferred from TREA to nBIM.
The switching of amines is necessary since the low boiling point of TREA prohibits efficient
separation of FA from TREA. The separated TREA is evaporated and obtained as the
top product, and the nBIM-formate product is sent to the FA purification column as the
bottoms product. Owing to the large boiling temperature difference of nBIM (248 °C) and
FA (100.8 °C), FA is efficiently separated as a top product of the purification column.
It should be noted that the original process design presented in the work by Park et al.
separately inject CO2 and the reaction amine, TREA, into the trickle-bed reactor, assuming
that the CO2 input is obtained as a purified form. However, since the FA-LOHC distribution
process analyzed in this study includes options for directly incorporating CO2 -captured
amine, the input stream to the tcFA process is assumed to be available in both forms.
Catalysts 2022, 12, 1113 11 of 21

Figure 2. Hydrogenation – process configurations

(a) Thermocatalytic FA production

(a)
TEA/H2O recycle

CO2
TEA H2
H2 O

Formic Acid
Thermocatalytic
reaction H2 recycle
120bar, 120℃

nBIM/FA recycle

Figure 2. Hydrogenation – process configurations

Trickle-bed reactor Evaporator Amine exchange column FA purification column
(b) Electrochemical FA production
(b)
Formic acid
N2
(recycled)
-- + WGS reactor
H2
(recycled)

Heat CO2
CO2 H2 exchanger (recycled)

N2

Electrolyzer

Water tank

PSA

Figure 7. The tcFA and ecFA production pathways via CO2 conversion. (a) Process flow diagram
for thermocatalytic CO2 hydrogenation to FA, and (b) process flow diagram for electrochemical
reduction of CO2 to FA.

3.1.2. Electrochemical CO2 Hydrogenation to FA

Compared to the tcFA process, the ecFA process is at an early stage of development.
The electrochemical reduction of CO2 to FA is a two-electron process, with a relatively low
equilibrium potential of −0.199 V vs. NHE, compared to other CO2 reduction products [15].
The recently proposed system by Fan et al. suggests the use of a PSE system for directly
obtaining purified FA via electrochemical CO2 reduction [26]. The proposed system pro-
duces formate at the cathode via CO2 reduction and protons at the anode via the hydrogen
oxidation reaction. The produced ions are then driven into the PSE layer by the electric
field, then recombined within the PSE to form FA. The produced FA is extruded using N2
gas, which allows easy separation of pure FA. While electrochemical reduction processes
have to be validated on a larger scale to consider the possibility of commercialization,
the contents of these studies show promising results for ecFA production, with stable
operations of over 100 h. Previous studies have suggested the production of formate via
electrochemical CO2 reduction within liquid electrolytes, requiring complex distillation
processes and extensive energy input for further purification of FA. The PSE-based FA
production process may enable early commercialization of the ecFA process due to efficient
and economical purification of FA. Thus, the PSE system is incorporated as the ecFA option
to be analyzed. The electrolyzer performance options are obtained from the Supplementary
Catalysts 2022, 12, 1113 12 of 21

Information of Fan et al. [26], and the overall process is formulated into a continuous form
by recycling the water input used for obtaining protons, and the water produced by the
side reaction, the reverse water-gas shift reaction. The operating parameters of the ecFA
system are shown in Table S2.
The ecFA process consists of three core units, the electrochemical reactor, the water-gas
shift (WGS) reactor, and the PSA unit. These three unit operations comprise the largest
portion of the process with respect to operational costs and CO2 emissions, and thus the
performance of these three sections greatly affect the overall performance of the ecFA
option. Thus, among the various options available for each unit, the most suitable option is
selected regarding performance and energy efficiency.
For designing the WGS reactor, the CuO-ZnO-Al2 O3 catalyst is selected to maximize
CO conversion. As presented in Pal et al. [27], the CuO-ZnO-Al2 O3 operates at low
temperatures of 200–250 °C, shifting the equilibrium towards more H2 production. Since
even trace amounts of CO existing within the product stream may be critical for the
application of H2 such as in fuel cells [27], it is important to select the WGS system with the
highest conversion of CO.
For the PSA system, the concept of integrating WGS catalysts into the PSA unit pro-
posed by Zhu et al. [28] was implemented. In the proposed system, high-temperature WGS
catalysts composed of Fe2 O3 and Cr2 O3 are implemented along with zeolite adsorbents,
to maximize the amount of H2 recovery and minimize CO output. The type of catalysts
used, the operating conditions, and the references for the incorporated WGS and PSA
systems are presented in Table S2.
Considering the operating conditions and unit performance of the electrolyzer, WGS
reactor, and PSA unit, the ecFA process is designed as shown in Figure 7b. The FA produced
from the electrolyzer is retrieved by liquefaction, and the remaining stream of water, CO,
and unreacted CO2 and H2 are sent to the WGS reactor. The production stream of the
WGS reactor is sent to the PSA unit to separate H2 and CO2 , which are recycled into the
electrolyzer for continuous operation. Prior to the PSA unit, a heat exchanger is installed to
recover the heat from the outlet stream of the WGS reactor, to enhance the energy efficiency
of the process. Note that the N2 , H2 , and CO2 recycle stream are represented in simplified
forms for better readability.

3.1.3. FA Dehydrogenation Integrated with CO2 Recovery

After being delivered to the site of usage, FA is dehydrogenated via a thermocatalytic
reaction to obtain H2 and CO2 . Since the emitted CO2 has to be returned to the FA
production site for reuse as an LOHC, the FA dehydrogenation process and the CO2
recovery process are modeled in an integrated form.
As for the dehydrogenation section, a recently proposed heterogeneous catalyst system
is considered. This is due to the fact that since it is not possible to selectively decompose FA
into CO2 and H2 with 100% selectivity, certain amounts of CO and H2 O are generated dur-
ing the dehydrogenation process, and the use of homogeneous catalysts during this process
requires additional catalyst regeneration for continuous operation. Since the addition of
distillation towers consequently consumes more energy, and because the column-included
process has not been studied or operated in previous studies or reports, using a homo-
geneous catalyst system would hinder the realistic analysis of the FA-LOHC distribution
system. Thus, to consider a process that is more likely to be realizable in the future, per-
formance indicators of state-of-the-art heterogeneous catalysts were incorporated into the
simulation model. As explained in the review by Xu et al. [29], recent research focus is
being made for the development of heterogeneous catalysts for liquid-phase FA dehydro-
genation. Of the various types of catalysts being developed, bimetallic catalysts, which
show enhanced FA dehydrogenation performance compared to the monometallic catalysts
due to the ensemble effect have recently gained spotlight and show high selectivity toward
H2 and CO2 production. In this study, the PdAu nanoparticle (NP) catalyst supported on
MSC-30 carbon, as presented in the study by Hong et al. [30], is assumed to be installed in
Catalysts 2022, 12, 1113 13 of 21

a continuous flow reactor of the dehydrogenation system. The proposed PdAu NP catalyst
dehydrogenates FA to H2 with near 100% selectivity at mild conditions of 60 °C, which
are important aspects required for designing an energy-efficient dehydrogenation process.
Since the performance of the PdAu NP catalyst in the long term is not presented within
the study by Hong et al. [30], a conservative value of 95% is used for FA to H2 selectivity.
Various parameters implemented for the dehydrogenation process design is provided in
Table S2.
Sequential to the dehydrogenation reactor, a WGS reactor is added to ensure a CO
concentration of less than 10 ppm. The catalysts used, the operating conditions, and the
performance indicators of the WGS reactor are identical to the WGS reactor used for ecFA
production, as explained in Section 3.1.2.
After the dehydrogenation step, two different options for CO2 recovery are considered
with regard to the transportation method of returning CO2 to the FA production site. One
is the separation of pure CO2 in liquid form using a PSA unit, and the other is the use of an
amine absorber to strip CO2 from the rest of the gases via amine-based CO2 capture.
In the option for using PSA to obtain liquefied CO2 , the incorporated catalysts and
operating conditions are identical to the specifications provided in Section 3.1.2. While
the output stream of H2 is sent to the compression unit for distribution, the CO2 stream is
integrated into heat exchangers for preheating other streams within the process. After heat
integration, CO2 is depressurized to 17 bar to meet the conditions for transport, and further
cooled down to −30 °C for liquefaction.
For the amine-based CO2 capture process, a conventional absorber column is consid-
ered, with a performance of 90% CO2 recovery. To directly incorporate the CO2 capture
process with the FA production process, a process using TREA as the capture amine is
proposed. Since no studies exist regarding the CO2 capture performance of TREA in an
absorber column, we performed CO2 capture experiments using an absorber column, using
3M TREA as the capture solvent. Images of the absorber column used for the experiment
are presented in Figure S1. According to the test results, CO2 absorption performance
was shown to be in the range of 87.1% to 95.1%, with respect to the different liquid-to-gas
(L/G) ratios tested. Detailed experimental results are provided in Table S4. Since the
CO2 capture performance of TREA was shown to be similar to that of monoethanolamine
(MEA), the capture rate of the TREA system is assumed to be 90%, in accordance with
the usual operational specification of MEA-based CO2 capture systems [31–33]. While the
concentration of CO2 is higher for the process streams compared to the experiment results,
the same capture performance can be achieved by using sufficient amounts of TREA. To this
end, the required amount of TREA is calculated according to the amount of CO2 emitted.
Since the TREA-captured CO2 can be transported at ambient conditions, no additional
operations for changing the temperature or pressure are required.
The process flow diagrams of the individual CO2 recovery processes integrated with
the FA dehydrogenation process are presented in Figure 8. To maximize the energy effi-
ciency of the processes, heat exchangers are added to integrate streams capable of energy
exchange. The outlet stream of the PSA unit in Figure 8a retains high temperature and
pressure, allowing effective preheating of process input streams. As for the TREA-based
CO2 capture system shown in Figure 8b, the outlet stream of the WGS reactor is 60 °C at
ambient pressure, and is used to preheat the input stream to the WGS reactor.
Catalysts 2022, 12, 1113 14 of 21
Figure 3. Dehydrogenation – process configurations

(b) FA dehydrogenation w/ CO2 liquefaction

(a)
H2O

Liquefied
CO2

H2

Formic acid

Figure 3. Dehydrogenation – process configurations

FA dehydrogenation WGS reactor PSA
reactor
(a) FA dehydrogenation w/ CO2 capture

(b)
Lean amine
H2

Formic acid Amine-absorbed

CO2

FA dehydrogenation WGS reactor CO2 absorber

reactor

Figure 8. Dehydrogenation of FA integrated with the two options available for processing CO2 –CO2
liquefaction and TREA-based CO2 capture. (a) Process flow diagram for dehydrogenation of FA
to produce H2 and liquefaction process of the produced CO2 stream. (b) Process flow diagram for
dehydrogenation of FA to produce H2 and use of TREA-based absorber column to retrieve CO2 from
the product stream.

3.1.4. Transportation Process

In the proposed FA-LOHC distribution system, it is assumed that the produced FA and
liquefied H2 are delivered to application sites in tank trailers driven by trucks. As shown in
Table 4, the transportation conditions for liquefied H2 , FA, and CO2 are different, and thus
different cost models are required for evaluating each option. For an accurate evaluation of
the costs considering the number of trucks required and the transportation schedule with
regard to the transportation capacity, the H2A Delivery Scenario Analysis Model (HDSAM)
is used. The relevant parameters referenced from the HDSAM 3.0 User’s Manual [34] are
provided in Table S3 of the Supplementary Materials (SM).

Table 4. Trailer conditions for the different chemicals delivered.

Chemical Name Temperature Pressure

Liquefied H2 −253 °C 1 bar
FA 25 °C 1 bar
Liquefied CO2 −30 °C 17 bar

With regard to the four different scenarios presented in Table 2, the number of trailers
required is different due to the difference in H2 compositions. As FA contains 4.4 wt% of
H2 , FA-LOHC systems require a greater number of trailers to deliver an equivalent amount
of H2 to the site of usage. Furthermore, since the recycled CO2 has to be delivered from the
site of usage, additional trailers for CO2 transportation have to be prepared. Thus, costs for
Catalysts 2022, 12, 1113 15 of 21

CO2 transportation trailers are added for scenarios 2–4. Moreover, for scenario 4, additional
transportation costs for TREA delivery are taken into consideration. During delivery of
FA, trailers containing TREA are driven to the usage site; after capturing CO2 using the
delivered TREA, the TREA-captured CO2 solution is recycled back to the production site.

3.1.5. H2 Liquefaction Process

Regarding the H2 liquefaction process, the parameters related to CAPEX, OPEX,
and environmental impacts are gathered from various reports and studies, rather than
designing a new process model. The overall cost parameters obtained from Chen [35]
are used. Details of the liquefaction process and the related parameters are presented
in Table S3. The incorporated cost model includes factors specific to the H2 liquefaction
process, such as cryogenic pump installation, and conversion process of ortho-hydrogen to
para-hydrogen, which is essential for minimizing H2 boil-off during transportation.
The CAPEX and OPEX of the liquefaction process are evaluated based on the results
by Connelly et al. [36]. The CAPEX of the installed liquefier is calculated as shown in
Equation (1), where N is the number of liquefiers required assuming 200,000 kg/d capacity
for a single liquefier, C1 is the liquefier design capacity in Mt/d, and CEPCI is the Chemical
Engineering Plant Cost Index for a specified year, used to reference the cost calculations to
a certain year.

Lique f ierCAPEX ($) = N × 1, 000, 000 × 5.6 × C10.8 × CEPCI (1)

Regarding the OPEX of a liquefier, a regression model with respect to the capacity is
developed based on the data points provided in Connelly et al. [36], and used to calculate
energy requirements. The regressed equation is shown in the equation below:

C2 −0.1
Lique f ierOPEX (kWh/kg) = 13.382 · ( ) (2)
1000
where C2 represents the liquefier capacity in units of kg/d.
In addition to the energy costs, additional costs for storage tanks, and liquefied H2
compression costs required during H2 distribution at the usage site, are considered with
parameters from Wulf and Zapp [37].

4. Methodologies
To evaluate the different scenarios of the FA-LOHC distribution options with regard
to profitability and sustainability, TEA and LCA are conducted. To obtain reliable results,
Aspen Plus simulation models developed for each step of every scenario are integrated with
Matlab to calculate the economical values, and the SimaPro software is used to evaluate
the environmental indices.

4.1. Techno-Economic Analysis (TEA)

4.1.1. Levelized Cost of Hydrogen
To evaluate the profitability of the different FA-LOHC distribution options, techno-
economic analysis is conducted for the individual options. Based on the developed Aspen
Plus simulation model for the FA production, transportation, dehydrogenation, and recycle
processes, a large-scale FA-LOHC distribution was designed by integrating the separate
sections according to the different scenarios. Assuming a plant life of 15 years and interest
rate of 15%, the net present values (NPVs), which represent the plant evaluation value at
the current period considering the CAPEX, OPEX, and sales cost, are evaluated. Equations
related to the calculation of NPV are provided in Equations (3)–(5), and parameters related
to the NPV calculations are presented in Table 1. While NPV values are appropriate
for analyzing the profitability of a given process, comparisons between different process
options can be better achieved by calculating the levelized cost of the product chemical.
Levelized cost refers to the cost of the product, which allows zero profit of the overall
Catalysts 2022, 12, 1113 16 of 21

plant, and is used as an indicator when evaluating newly developed CCU plants [38].
In this study, the LCOH, which is the cost of the H2 provided to the HRS site, is calculated.
As shown in Equation (6), the LCOH is calculated by finding the H2 cost that drives the
overall NPV to zero.

NE = (1 − tincome ) · (S − CExcl.Dep. − CD ) (3)

CF = ( NE + CD ) − CTPI (4)
CFn
NPV = ∑ (5)
(1 + i ) n
NPV ( LCOH ) = 0 (6)

In the above equations, NE stands for the net earnings, and CF represents the annual
cash flow. tincome represents the income tax, S is the sales profit, CExcl.Dep. is the production
cost exclusive of depreciation, CD is the cost depreciation, and CTPI is the total permanent
investment cost, which includes the total depreciable capital and non-depreciable capital
such as the cost of land and start-up operations.
For CAPEX and OPEX calculations, the process unit costs and utility values are obtained
from Seider et al. [39], and values for specific units such as WGS reactors and PSA columns,
are obtained from the related studies [27,28,40,41]. Note that for modeling and cost evaluation
of the reactors, equilibrium models were used, assuming that the reactor performance is
maintained after scale-up, and the increased dimensions, catalyst, and packing usage, were
calculated within the cost model. Regarding the cost calculation of the electrolyzer used in
ecFA, the method used in Na et al. [38] is implemented, where a proton exchange membrane
(PEM) electrolyzer is assumed and the cost of catalysts and electrodes are changed propor-
tionally to the cost of the metals. Details on the electrolyzer cost calculation are provided in
the Supplementary Materials. It should be noted that since the cost evaluations from different
studies are based on different periods, it is necessary to adjust the values so that the costs are
calculated on a common basis. Thus, the CEPCI of 2020 is used to convert the values from
different periods to values with reference to 2020 US dollars.

4.1.2. Global Sensitivity Analysis

Since the developed FA-LOHC distribution system is subject to many uncertainties,
including utility or material costs, transportation distance, production capacity, or prac-
tical difficulties, which may occur during actual construction of the plant, it is essential
to conduct sensitivity analyses of the relevant parameters on the overall profitability of
the system. While local sensitivity can provide the overall range of the profitability with
respect to a single parameter, it fails to apportion the individual contributions of the various
parameters to the cost of the overall system, especially when the parameters are highly
correlated [38,42]. Thus, in this study, the variance-based GSA is applied to evaluate the ef-
fects of parameter variation on the economic performance of each scenario. Variance-based
GSA calculates the variance change inferred from the parameter changes, and evaluates
the relative contribution of each parameter to the cost. In this study, to alleviate the compu-
tational burden of evaluating the GSA indices for all combinations of the parameter set,
the first-order GSA index for each of the parameters are calculated first, then parameters
which require further evaluation of complex order indices are considered. The first order
GSA index (Sobol index) is calculated using the FAST method suggested by Cannavo [42],
as shown in Equation (7):
var [ E(y| xi )]
Si = (7)
var (y)
where var (y) represents the variance of the output, and var [ E(y| xi )] represents the variance
of the expectation of y given that a set of variables xi is fixed.
Catalysts 2022, 12, 1113 17 of 21

4.2. Life Cycle Assessment

LCA evaluates the environmental impact of a given process, regarding various impact
factors such as GWP, FRS, etc. Based on the international standards ISO 14040 [43] and
14044 [44], LCA analyzes the environmental impact of a defined functional unit within a
specified system boundary. Since the main objective of LCA conducted in this study is to
compare the different hydrogen distribution options, a cradle-to-gate analysis is conducted
where the system boundary is defined from the raw material supply for producing FA,
to the final delivery of H2 to the place of application, which is the HRS site. This is a
reasonable assumption since the downstream application of the delivered H2 is exactly
the same for the different scenarios, and these types of simplifications are made in various
CCU studies [23,45,46].
A schematic overview of the system boundary is presented in Figure 9. It is worth
noting that for an accurate evaluation the source of CO2 is included within the system
boundary via the system expansion approach, which is assumed as an ammonia production
plant. This is in accordance with the guidelines provided in the literature for LCA of CCU
processes, where the inclusion of CO2 sources are recommended to allow a fair comparison
between different pathways [23,45,46]. Thus, the final functional unit is the production
of 1 kg of H2 and 0.45 kg of ammonia for all of the cases considered. As presented in
Figure 9, the ammonia plant is included within the system boundary of the liquefied
H2 distribution system, to compensate for the amount of CO2 utilized in the FA-LOHC
distribution system. Life cycle inventories, including utility and materials are mostly
obtained from the Ecoinvent v3 database [47,48]. For the items that are missing from the
Figure 5. LCAdatabase,
analysis impact factors are obtained from other references or approximated from materials
that have similar properties compared to the material of interest. After collecting all of
the inventories,
Green H2
the environmental impact factors are evaluated using the ReCiPe 2016
Figure 5. LCA analysis
Midpoint System boundary
Hierarchical method for liquefied
[49].H transportation2

H2 Transportation Process

Liquefaction
(a)
LH2 Trailer Transport Gasification &
Green H2
Ammonia Compensation Compression
System boundary for liquefied H2 transportation 1kg H2
Conventional ammonia H2 Transportation Process
Electricity Catalyst (99.99%, 900bar)
IONEX cat. Refrigerant
plant without CO2 Refrigerated Fuel
capture Electricity
Trailer
Gasification &
Liquefaction LH2 Trailer Transport
Ammonia Compensation Compression

0.45kg1kg
NHH32
Conventional ammonia Electricity Catalyst (99.99%, 900bar)
IONEX cat. Refrigerant
plant without CO2 Refrigerated Fuel
capture Electricity
Trailer

0.45kg NH3

(b)
Green H2
System boundary for FA-LOHC transportation cycle

FA-LOHC Transportation Process

CO2

Green H2
CO2 source System boundary for FA-LOHC transportation cycle Dehydrogenation &
FA Production FA Transportation
Compression 1kg H2
Ammonia plant FA-LOHC Transportation Process
(99.99%, 900bar)
CO2
Steam Refrigerant Trailer Fuel Steam Refrigerant
Flue gas
CO2 source Materials/ Dehydrogenation
Electricity
FA Production FA Transportation Electricity Catalyst &
Catalysts Compression
Ammonia plant 1kg H2
(99.99%, 900bar)

Steam Refrigerant Trailer Fuel Steam Refrigerant

Flue gas
Figure 9. System boundaries for the two different H2 distribution systems. (a) System boundary
Materials/
Electricity Electricity Catalyst
for the liquefied H2 distribution system.Catalysts
An ammonia plant is included by the procedure of system
expansion to compensate for the CO2 production source, and (b) system boundary for the FA-LOHC
distribution system. An ammonia plant is included as the source for CO2 .

5. Conclusions
In this study, the potential of using FA as an LOHC to promote the hydrogen economy
was comprehensively analyzed regarding state-of-the-art FA production technologies and
Catalysts 2022, 12, 1113 18 of 21

realistic scenarios. The overall FA-LOHC integration cycle was divided into four sections,
namely the FA production, transportation, dehydrogenation of FA, and recycle of the base
chemical CO2 , and each of the processes were designed using the simulation software
Aspen Plus, then their economic and environmental potential were evaluated with respect
to the liquefied H2 distribution system. Considering the economical aspect, the tcFA-based
scenarios were shown to be in an earlier stage to surpass the performance of liquefied H2
due to the large amounts of energy consumption during FA production. Further investiga-
tion of process optimization and new amines with better solubility with water could allow
the tcFA-based process to be developed as a feasible FA-LOHC component. The ecFA-
based scenario showed better performance economically compared to the liquefied H2
distribution, owing to the small amounts of steam usage and simple separation processes
as compared to the tcFA process. However, the electrolyzer system is not affected by the
economy of scale, and showed a sharper increase in cost compared to the tcFA process
with regard to an increase in the H2 distribution capacity. To improve the economical
performance of the ecFA system, improvements for catalysts or electrolyzer systems are
necessary, to increase the FE and decrease the relative contribution of the electrolyzer costs.
Considering LCA, all FA-LOHC scenarios showed poor performance compared to the
liquefied H2 distribution system due to the large impacts incurred by the FA production
process. As FA contains H2 at a weight ratio of 4.4%, the larger use of energy, and accord-
ingly high environmental impact, is inevitable. This could be overcome in the future with
the growth of the FA-LOHC market, where extensive amounts of CO2 can be fixed within
the FA-LOHC cycle, while being used for H2 distribution. Thus, further studies regarding
the efficient production of FA and dehydrogenation processes are required to incorporate
the FA-LOHC system into the real world.

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

10.3390/catal12101113/s1, [9–11,24,26–28,30,34,37–39,50,51]. Supplementary data related to this
work are provided in a separate document. Figure S1. CO2 absorber tower used for TREA CO2
capture experiments. Table S1. Process operating conditions and parameters used for designing
the tcFA process [1]. Table S2. Process operating conditions and parameters used for designing the
ecFA process [2–5]. Table S3. Process operating conditions and parameters used for designing the
liquefied H2 distribution system [6–8]. Table S4. CO2 absorption experiment results using TREA as
the capture amine.
Author Contributions: Conceptualization, C.K. and K.K.; methodology, C.K.; software, C.K., K.K.
and Y.L.; writing—original draft preparation, C.K.; writing—review and editing, C.K., K.K., Y.L.
and U.L.; supervision, U.L.; funding acquisition, U.L. All authors have read and agreed to the
published version of the manuscript.
Funding: This work was supported by the National Research Foundation of Korea (NRF) grant
funded by the Korean government (MSIT) (no. NRF-2020M3H7A1098259).
Data Availability Statement: The data presented in this study are available in the Supplementary Materials.
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations
The following abbreviations are used in this manuscript:

CCUS Carbon Capture, Utilization, and Storage

LOHC Liquid Organic Hydrogen Carrier
FA Formic Acid
FA-LOHC FA-based Liquid Organic Hydrogen Carrier system
HRS Hydrogen Refueling Station
PSE Porous Solid Electrolyte
NP Nanoparticle
Catalysts 2022, 12, 1113 19 of 21

L/G Liquid-to-Gas
LCOH Levelized Cost of Hydrogen
TEA Techno-Economic Analysis
GSA Global Sensitivity Analysis
CAPEX Capital Expenditure
OPEX Operational Expenditure
HDSAM H2A Delivery Scenario Analysis Model
LCA Life Cycle Assessment
GWP Global Warming Potential
FRS Fossil Resource Scarcity
TREA Triethylamine
MEA Monoethanolamine
ecFA electrochemical FA production
tcFA thermocatalytic FA production
NPV Net Present Value
CEPCI Chemical Engineering Plant Cost Index
WGS Water-Gas Shift
PSA Pressure Swing Adsorption

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