Young Suk JoKorea Institute of Science and Technology
AIChE, 2018.10.31
Ammonia as an Efficient COX-free Hydrogen Carrier:
Fundamentals and Applications
1. Hydrogen Energy
2. Ammonia as an Efficient COX Hydrogen Carrier
3. Technical Applications
Hydrogen Energy
H2
2013 2014 2015
NEXO
2018
609 km of Driving range
“Korean government expects 5000 H2 stations by 2030”
Congress R&D Meeting(’18.03.30)
Clarity
MIRAI
Tucsan
Elements on Earth
Oxygen
47%
Silicon
28%
Al 8%
Fe 5%
Others
12%
Nitrogen
78%
Oxygen
21%
Ar 0.9%
Trace 0.1%
Energy Density of Hydrogen
U.S. Department of Energy
Research Motivation
Production
Storage
Utilization
Hydrogen Society - Final Goal
Excess renewable E
BatteryESS
for < MWh
Wind
Electrolyzer Power Transportation
H2
Solar
E-Chemicals/Chemicals(e.g., eH2,
eNH3, eMeOH)
H2O, N2/H2O
CO2/H2O
Fuel Cells
Fossil FuelsReforming
P2L
H2
P2G
(e.g., CH4)
e-
Transportation
CCS
ConventionalRenewable
House
Ammonia as a H2 Carrier
ReleaseStoreHydrogenation
NH3
N2
➲ Well-developed NH3 synthesis process ( Haber-Bosch )
➲ Easy storage (0.8 MPa, 20 ℃, liquid) & transportation
➲ High hydrogen contents ( 17.7 wt%, 108 gH2/ L(l) )
No further emission of CO2)
Dehydrogenation
Electrolysis PEMFC
Ammonia to Hydrogen
N2NH3
H2NH3
NH3Decomposition
H2Purification
NH3Removal
• On-site power generation• Hydrogen station
High-purityHydrogen
COX-free Power-pack fueled by NH3
Chem E (NH3) Fuel CellReformer
Chem E (C4H10) Combustor
Heat E (Heat)
Cham E (H2)
Applications
Electrical E
Jo. Y., et al., Applied Energy 224:194-204, 2018
Catalyst Development
Jo. Y., et al., Applied Energy 224:194-204, 2018
Surface area
(m2/g)
Pore size
(cm3/g)
Pore
diameter
(Å)
Al2O3 155.3 0.52 129.5
La(10)-Al2O3
145.8 0.60 160.5
La(20)-Al2O3
95.62 0.46 188.8
La(30)-Al2O3
59.47 0.28 184.5
La(40)-Al2O3
47.30 0.22 176.9
La(50)-Al2O3
35.76 0.17 189.3
La doped Al2O3 LaAlO3 (perovskite phase)
La mol (↑) Surface area, Pore size (↓)
Catalyst Evaluation
Jo. Y., et al., Applied Energy 224:194-204, 2018
➲ 10 or 20 mol% of La promoted Al2O3 showed activities
➲ La(10)-Al2O3 density 0.55 g/mL , La(20)-Al2O3 density 0.78 g/mL
➲ Select Ru2 wt%/La(20)-Al2O3
Reactor Development
Jo. Y., et al., Applied Energy 224:194-204, 2018
> 99.7% Conversion
Amount of H2 produced>800 L (2.6 kWh)
➲ Stable operation for about 60 min at 550 ℃(currently ~ 7 months durability tested)
➲ Energy efficiency 70%
Adsorbent MaterialsCapacity
(mmol NH3/g)
13X zeolite 3.08
HY zeolite 1.31
HZSM-5 zeolite 0.23
10 wt% Mg-Al2O3 0.46
10 wt% Ca-Al2O3 0.38
System Process Design
Jo. Y., et al., Applied Energy 224:194-204, 2018
1 kW PEMFC
13X Zelolite
Ru/La-Al2O3
Reactor
System Integration
Jo. Y., et al., Applied Energy 224:194-204, 2018
0 20 40 60 80 100 120
0
200
400
600
800
1000
1200
Fu
el C
ell P
ow
er
Ou
tpu
t (W
)
Time (min)
Butane + Hydrogen
> 2.3kWh
NH3 9L/min [ 32A, 32.7V ]
Power Generation Demonstration
Efficiency Analysis
Jo. Y., et al., Applied Energy 224:194-204, 2018
Reformer: ~ 63 %System: ~ 31%
2 3 4 5 6 7 8
35
40
45
50
55
60
Reformer Efficiency
System Efficiency
NH3 Feed rate (L min
-1)
Re
form
er
Eff
icie
nc
y (
%)
18
20
22
24
26
28
30
32
34
Sy
ste
m E
ffic
ien
cy
(%
)
➲ Reformer ηNH3 feed rate, heat source/transfer
➲ System η Waste H2 recovery
NH3 to H2 to Electricity - Best Efficiency Reported
Jo. Y., et al., Applied Energy 224:194-204, 2018
6 10 14 18 22
20
25
30
35
40
45
50
Sy
ste
m E
ffic
ien
cy
(%
)
Current Loaded (A)
Hydrogen
Butane + Hydrogen
Butane
(b)
OriginalReformer Efficiency: ~ 63 %System Efficiency: ~ 31%
Improved~ 84 %~ 49 %
Electricity from Ammonia
Jo. Y., et al., Applied Energy 224:194-204, 2018
0 50 100 150 200 250 3000
1
2
3
4
5
6
7
8
System weight (kg)
Gra
vim
etr
ic h
yd
rog
en
cap
acit
y (
gH
2/g
syste
m)
0
10
20
30
40
50
60
Vo
lum
etr
ic h
yd
rog
en
cap
acit
y (
gH
2/L
syste
m)
ReactorCatalyst
Ammonia Tank
Power Pack Packaging
PEMFCUS DOE target
(onboard automotive H2 storage)
➲ 3.4 wt% system based (with heavy NH3 tank)
➲ 4.9 wt% expected (with light NH3 tank)
Jo. Y., et al., Applied Energy 224:194-204, 2018
Tethered Drone Application
First Flight Test
Duration Test
Ammonia Energy Scenarios
Renewable Hydrogen
2018.07.13“Liquid sunshine: Ammonia made from sun, air, and water could turn Australia into a renewable energy superpower,”
2018.05.03
2018.08.08
NH3 to H2 using Membrane Reactor
Membrane
Catalyst
MR(Simultaneous reforming + purification)
MemCatalyst
Reforming Purification
Novel NH3 MR Concept
Jo. Y., et al., Journal of Power Sources 400:518-526, 2018
Membrane and Membrane Reactor
Jo. Y., et al., Journal of Power Sources 400:518-526, 2018 Jo. Y., et al., Seperation and Purification Technology 200:221-229 (2018)
Jo. Y., et al., Applied Energy 224:194-204, 2018
Performance Improvements
Jo. Y., et al., Journal of Power Sources 400:518-526, 2018
Comparisons
Jo. Y., et al., Journal of Power Sources 400:518-526, 2018
암모니아 분리막 반응기
Jo. Y., et al., Journal of Power Sources 400:518-526, 2018
Ammonia: What needs to be done?
Novel Strategy: H2 as a Heat Source
Jo. Y., et al., Applied Energy 224:194-204, 2018
𝑆𝐿 ~ 180 𝑐𝑚/𝑠
𝑆𝐿 ~ 35 𝑐𝑚/𝑠