ammonia as an efficient cox-free hydrogen carrier ......fundamentals and applications. 1. hydrogen...

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


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


➲ 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


> 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


1 kW PEMFC

13X Zelolite

Ru/La-Al2O3

Reactor

System Integration


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


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


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


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)


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)


Performance Improvements


Comparisons


암모니아 분리막 반응기


Ammonia: What needs to be done?

Novel Strategy: H2 as a Heat Source


𝑆𝐿 ~ 180 𝑐𝑚/𝑠

𝑆𝐿 ~ 35 𝑐𝑚/𝑠

ammonia as an efficient cox-free hydrogen carrier ......fundamentals and applications. 1. hydrogen...

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