绿氢制甲醇
绿氢制甲醇
绿氢制甲醇
ScienceDirect
Article history: Alkaline water electrolysis which is the most commercialized and mature technology of
Received 20 September 2022 water electrolysis was researched to improve performance by the Korea Institute of Energy
Received in revised form Research (KIER). In line with the trend of energy shift, renewable urea production through
18 December 2022 hydrogen production from alkaline water electrolysis was proposed in this work. To vali-
Accepted 5 January 2023 date the process modeling of renewable urea production and hydrogen performance
Available online 31 January 2023 analysis with IeV curves was assessed. Economic and life cycle assessments were
* Corresponding author. School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology, 50 UNIST-gil,
Eonyang-eup, Ulju-gun, Ulsan 44919, Republic of Korea.
E-mail address: [email protected] (H. Lim).
https://doi.org/10.1016/j.ijhydene.2023.01.062
0360-3199/© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 6 1 4 8 e1 6 1 5 8 16149
Keywords: conducted to provide quantitative guidelines for renewable urea production. Absolutely,
Urea production the influential factor of unit urea production cost was hydrogen from alkaline water
Renewable energy electrolysis and environmental assessment results as well. Moreover, the guidelines for
Alkaline water electrolysis renewable urea production were provided through cost estimation and life cycle assess-
Process simulation ment. In summary, hydrogen production from alkaline water electrolysis had a significant
Economic analysis impact on urea production and for this reason, research on alkaline water electrolysis
as low-priced catalyst as nickel or stainless steel and a high whereas previous work was focused on the analysis of
lifetime of the system of 10e20 years [15e17], renewable urea experiment and process simulation. Also, the guidelines for
production would be performed with high performance renewable urea production from green H2 could be obtained
compared with other water electrolysis system as polymer under comprehensive analysis.
electrolyte membrane water electrolysis and solid oxide
electrolysis. Thus, alkaline water electrolysis has become the
most commercialized compared to other water electrolysis Methods
[17e19]. However, the volume of equipment is increased
since the operating current density is lower than polymer Process modeling
electrolyte membrane water electrolysis [20,21], also, alkaline
water electrolysis has many downsides like slow start and To produce the renewable urea, the process simulation of the
stop responsiveness, unfavorable under high pressure, and alkaline water electrolysis system and urea production was
differential pressure conditions [22,23]. Therefore, further performed by ASPEN PLUS® simulator and the calculator
studies on the effect of H2 production from alkaline water function in ASPEN PLUS® was utilized for the alkaline water
electrolysis based on experimental results from the Korea electrolyzer stack. Fig. 1 shows the process flow diagram of
Institute of Energy Research (KIER) were performed for renewable urea synthesis including H2 from alkaline water
renewable urea production with regard to technical, eco- electrolysis.
nomic, and environmental perspectives. The comprehensive At first, the reactant of the alkaline water electrolyzer
analysis of renewable urea production from H2 through made up of H2O and potassium hydroxide (KOH) was calcu-
alkaline water electrolysis considering economic and envi- lated using the calculator at 25 C, 1 bar, and 30 wt% of KOH.
ronmental perspectives was assessed with experimental Especially, the mass flow rate of the reactant can be estimated
results of alkaline water electrolysis. In this work, the inte- based on Equation (1), which is a function of faradaic effi-
grative analysis of renewable urea production was conducted ciency, current density, and active cell area [24].
Fig. 1 e Process flow diagram of renewable urea production combined with alkaline water electrolysis system for green H2
production. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this
article.)
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CD ¼ 2:47 9:832 ðFG Þ0:8 (11) Table 2 e Experimental results of the alkaline water
electrolysis stacks from the Korea Institute of Energy
0:82
WCP Research (KIER).
CCP ¼ 8; 650 (12)
hCP Parameter Value Unit
where FG is the feed rate (kg s1) of gas into the drum, WCP is Operating temperature 80
C
compressor power (hp), and hCP is the efficiency of the Operating pressure 7 bar
compressor (%). For reactant such as N2, H2O, and captured Potential 1.8 V
Current density 0.8 A cm2
CO2, respective unit price are 0.01 [31] ($ kg1), 0.067 ($ ton1),
Cell radius 100 cm
and (50e100 $ ton1) [32], respectively. Supplement cost is
Number of cell for stack 200 Cells
estimated by assuming 20% of the sum of capital costs [33]. Faradaic efficiency 82 %
Respective labor, maintenance, and other costs are calculated Cell efficiency 82 % (HHV)
by assuming 0.3% [34], 2% [33], and 1% [33] of the sum of capital Number of stack 5 Stacks
costs, respectively. Annual costs are evaluated considering the KOH concentration 30 wt%
capital recovery factor (CRF) as follows (Eq. (13)) [35].
pð1 þ pÞn
CRF ¼ (13)
ð1 þ pÞn 1 Firstly, the performance of H2 production was 0.85 kg hr1
under the operating conditions as above mentioned. The
where n is the project period and p is the discount rate.
performance of H2 production for the KIER model under
Moreover, unit urea production cost could be obtained by
operating conditions of commercial electrolyzers was per-
dividing the sum of annual cost ($ y1) by urea production
formed (Fig. S1 eFig. S11).
capacity (kg y1).
Overall, the operating temperature between 65 and 90 C
Life cycle assessment was designed and the scales of operating pressure were widely
distributed as 5e32 bar. General trend of IeV curves, which
Life cycle assessment is performed for investigation of envi- data gained from Buttler et al. [39], was shown increasing
ronmental impact through gathering literature and analysis. voltage with increasing current density. To compare the in-
Through the four steps: 1) goal and scope definition, 2) making dividual results of the supplier with the results of KIER, each
an inventory, 3) impact assessment method application on the supplier of alkaline water electrolysis was listed as DLR, FZ
result, and 4) interpretation of results, life cycle assessment is Julich HPEL, Lurgi, GHW, Metkon Alyzer, FZ Julich (Phoebus),
conducted [36]. For these results, four ISO standards are Stuart Energy, Casale Chemicals, HT-Hydrotechnik, Hydro-
covered ISO 14040 for common principles, ISO 14041 for goal genics, ELB (Lurgi). Most of the suppliers of alkaline water
and scope definition, ISO 14042 for impact assessment, and electrolysis were shown that cell voltage at a current density
ISO 14043 for interpretation [37]. SimaPro (9.1.1.7) is a life cycle of 0.4 A cm2 varies between 1.7 and 2.1 V except HT-
assessment software to analyze the environmental aspects of Hydrotechnik. As an exception of HT-Hydrotechnik, the sup-
products or services. SimaPro (9.1.1.7) supports environ- plier has high overpotentials with a low current density of
mental product declarations, greenhouse gas, and interna- 0.25 A cm2. Like all the alkaline water electrolysis have in
tional reference life cycle data system (ILCD) handbook, which common, the performance of H2 production rate was
the document provides technical guidance for life cycle increased with increasing voltage and increasing current [40];
assessment with specific criteria and guides. The Swedish also, production rate was decreased with increasing current
environmental product declaration impact assessment density given that high energy consumption and low effi-
method is used for SimaPro software. Contributions of energy, ciency of production [41]. However, the process simulation
transport, waste, and other parts of the production system are model applied experimental results from KIER indicated that
allowed for new grouping functions following product cate- the H2 production rate maintained an increasing tendency.
gory rules. Also, SimPro provides various impact categories as Because some experimental aspects such as durability, life-
well: non-renewable resources and renewable resources, time, and load range were not considered for the model.
global warming, acidification, ozone layer depletion, photo- Through the performance of H2 production with IeV curves,
chemical oxidant formation, and eutrophication. ReCiPe 2016 the guidelines of H2 production rate would be obtained under
Midpoint (H) is applied for environmental assessment as the the operating conditions of each supplier except for durability
method in this boundary system [38]. In addition, Ecoinvent 3 and some experimental aspects, only assuming that have
e allocation, cut-off by classification e system is considered in ideal conditions.
this system. The system boundary was cradle to gate and the
Economic assessment of renewable urea production
functional unit was kg-urea1.
Fig. 2 e Effects of stack performances considering system voltage and current density on renewable urea production rates.
current density increased and voltage was fixed, the urea H2 production costs and electricity prices significantly impact
production rate also increased as well. The urea production urea production, and the commercialization of large-scale
rate shows the same tendency as the performance of the H2 processes is expected to reduce prices.
production rate. As aforesaid, the tendency was presented due
to the high effects of H2 on urea production. Environmental assessment of renewable urea production
At urea production capacity of 0.18 ton d1, itemized cost
estimation was performed and the result shows that the The system boundary of life cycle assessment is primarily a
process has an obvious key factor as H2 production cost; cradle-to-gate examination technique to inspect detailed
therefore, the pie diagram was shown except hydrogen factor. processes and products. Based on process simulation results,
And considering that the compressor (39.56%), electricity SimaPro (9.1.1.7) database was used, and the environmental
(18.3%), and captured CO2 (15.88%) were the main parameters impact of 1 kg urea generation was chosen as the functional
of the process. Fig. 3 presents the cost estimation of unit urea unit. Figures present the detailed global warming results of
production as capacity grows as 0.18, 1, 5, 10, 50, and 100 ton renewable urea production containing several information on
d1. At the capacity of 0.18 ton d1, cost estimation was materials (Figs. 4e6).
calculated as 141.88 $ kg1; however, at the 100 ton d1, the The cell stack construction consists of a multifarious life
result was reduced to 11.75 $ kg1 due to economies of scale. cycle inventory with copper, steel, nickel, aluminium,
Fig. 3 e Cost estimation results for unit urea production cost with various renewable urea production capacities.
16154 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 6 1 4 8 e1 6 1 5 8
Fig. 4 e Climate change impact of cell stack construction for alkaline water electrolysis under cradle-to-gate system
boundary.
polyphenylene sulfide, polysulfone, N-methyl-2 pyrrolidone, 1.24 kgCO2eq kg1 for NH3 generation. Table S2 indicates the
zirconium oxide, carbon monoxide, water, industrial machine, inventory for 1 kg of Haber-Bosch process from H2 obtained
plaster mixing, calendaring, electricity, and heat. Among through alkaline water electrolysis. For renewable urea pro-
them, steel, nickel, aluminium, N-methyl-2-pyrrolidone, duction, the Haber-Bosch process as previously stated, and
water, electricity, and heat were influential factors as 0.018, captured CO2 from the coal power plant was considered.
0.033, 0.0010, 0.00087, 0.0043, 0.438, and 0.001 kgCO2eq kg1 of Especially, the inventory of captured CO2 from the coal power
respective value for global warming. Definitely, the highest plant was obtained from Koornneef et al. [42]. The captured
value is 0.438 kgCO2eq kg1 as an electricity factor for cell stack CO2 process containing CO2 capture infrastructure,
construction. Thus, the result of the global warming potential compressor infrastructure, onshore pipeline infrastructure,
of cell stack construction is 0.498 kgCO2eq kg1, in total. Table CO2 injection facility, and pulverized coal power plant infra-
S1 shows the inventory for 1 kg of cell stack construction. The structure was considered for life cycle assessment. Table S3
electricity resource was apparently taken up as the main shows an entire inventory of renewable urea production
component even though various primary component was including captured CO2 from the coal power plant.
made up for cell stack construction. The renewable urea production process considering cell
Fig. 5 shows the result of global warming potential for the stack construction, the Haber-Bosch process for NH3 synthe-
Haber-Bosch process from H2 production through the alkaline sis, and captured CO2 from the coal power plant was assessed
water electrolysis process. The Haber-Bosch process from H2 to determine the total global warming results. Renewable urea
production through alkaline water electrolysis consists of ni- production consists of the Haber-Bosch process from H2 pro-
trogen, iron ore, operation, electricity, and cell stack con- duction through alkaline water electrolysis, pulverized coal
struction of alkaline water electrolysis. The cell stack power plant infrastructure, and captured CO2 process with
construction which is in charge of H2 production was a key CO2 capture infrastructure, CO2 compressor infrastructure,
factor as 1.18 kgCO2eq kg1 for global warming impact. Also, onshore CO2 pipeline infrastructure, and CO2 injection facility.
the electricity used for alkaline water electrolysis was a potent In terms of the environmental aspect, the Haber-Bosch pro-
factor as well. Respective value of global warming potential is cess for NH3 synthesis was the most influential factor for
Fig. 5 e Climate change impact of ammonia production from Haber-Bosch process with alkaline water electrolysis under
cradle-to-gate system boundary.
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Fig. 6 e Climate change impact of renewable urea production with alkaline water electrolysis under cradle-to-gate
boundary.
renewable urea production because the respective value of for global warming (88%), stratospheric ozone depletion
global warming result was 0.72 kgCO2eq kg1. Overall, 0.725 (84.8%), ionizing radiation (97.6%), ozone formation (78.4%),
kgCO2eq kg1 was the global warming result for renewable freshwater eutrophication (90%), marine eutrophication
urea production. Renewable urea production was affected by (86.3%), human carcinogenic toxicity (65.2%), land use (85.5%),
cell stack construction for alkaline water electrolysis in terms and fossil resource scarcity (88.2%). Definitely, electricity is a
of environmental aspects. To reduce the global warming significant factor that can affect a lot of the environmental
value, electricity has to draw from more renewable resources side. The results of the environmental impact assessment will
such as solar energy, wind energy, biomass, hydropower, and be changed a lot if the source of electricity changes. Secondly,
geothermal power. the nickel material was a substantial factor in fine particulate
On the whole, life cycle impact assessment was investi- matter formation (54.7%), terrestrial acidification (62.5%),
gated with perspectives of global warming, stratospheric terrestrial ecotoxicity (83.4%), freshwater ecotoxicity (52.1%),
ozone depletion, ionizing radiation, ozone formation, fine marine ecotoxicity (51.6%), and mineral resource scarcity
particulate matter formation, terrestrial acidification, fresh- (86.9%).
water eutrophication, marine eutrophication, ecotoxicity, The cell stack construction was the dominant factor for all
human carcinogenic toxicity, land use, mineral resource characterization in terms of environmental aspects; it means
scarcity, fossil resource scarcity, and water consumption. that the electricity used for alkaline water electrolysis had
From the results (Fig. 7), electricity was the dominant factor affected ammonia production. Especially, nitrogen used for
Fig. 7 e Life cycle assessment results in terms of diverse environmental characterizations of cell stack construction for
alkaline water electrolysis.
16156 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 6 1 4 8 e1 6 1 5 8
Fig. 8 e Life cycle assessment results in terms of diverse environmental characterizations of ammonia production with
alkaline water electrolysis.
the ammonia production process significantly impacted production, respectively. The cell stack construction was a
various environmental terms when the cell stack construction high impact on several characteristics of the environmental
was excluded. Expectably, electricity was also the predomi- impact such as global warming, stratospheric ozone, ionizing
nant item except for alkaline water electrolysis unit as follows radiation, ozone formation, freshwater eutrophication, ma-
Fig. 8. Consequently, the alkaline water electrolysis unit as a rine eutrophication, human carcinogenic, land use, and fossil
H2 production system was an influential item in terms of resource scarcity for life cycle assessment. In terms of eco-
economic and environmental perspectives, both of them. nomic and environmental perspectives, alkaline water elec-
trolysis as a clean hydrogen production method was a highly
dominant impact on renewable urea production. Develop-
Conclusions ment of renewable urea production with regard to economic
and environmental aspects could be achieved with the tech-
The proposed concept was renewable urea production with nological development of alkaline water electrolysis.
hydrogen production through alkaline water electrolysis
based on experimental results from the Korea Institute of
Energy Research (KIER). The concept was investigated from Declaration of competing interest
economic and environmental perspectives. Technical anal-
ysis, itemized cost estimation, scaled-up cost estimation, and The authors declare that they have no known competing
life cycle assessment for renewable urea production were financial interests or personal relationships that could have
performed, totally. The analyses were conducted based on appeared to influence the work reported in this paper.
process simulation using ASPEN PLUS® for the performance of
hydrogen and urea production. The performance of the
hydrogen production rate was increased with increasing
Acknowledgment
voltage and current; also, the production rate was decreased
with increasing current density due to high energy con-
This research was supported by the Hydrogen Energy Inno-
sumption and low efficiency of production. In addition, the
vation Technology Development Program of the National
urea production rate was increased with increasing voltage
Research Foundation of Korea funded by the Korean govern-
and fixed current density; also, the opposite case as well.
ment (Ministry of Science and ICT (MSIT)) [NRF-
Respective unit urea production costs were 141.88, 70.77,
2019M3E6A1064290], the National Research Foundation of
37.26, 28.31, 15.15, and 11.75 $ kg1 for urea production ca-
Korea grant funded by the Korea government [NRF-
pacity of 0.18, 1, 5, 10, 50, and 100 ton d1. Also, compressors,
2019M1A2A2065614], and the Carbon Neutrality Demonstra-
captured CO2, and electricity were significant items for
tion and Research Center of UNIST (Ulsan National Institute of
renewable urea production when hydrogen production from
Science and Technology).
alkaline water electrolysis as the predominant factor was
excepted. Global warming potential was assessed for cell
stack construction, the Haber-Bosch process from hydrogen Nomenclature
production through alkaline water electrolysis, and renewable
urea production, respectively. Individual values are 0.498, KIER Korea Institute of Energy Research
1.24, and 0.725 kgCO2eq kg1 for cell stack construction, the ILCD International reference life cycle data system
Haber-Bosch process for NH3 synthesis, and renewable urea FE Faradaic efficiency (%)
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 6 1 4 8 e1 6 1 5 8 16157
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