Reactor Technologies for Carbon-Neutral Solar Fuels and Clean Vehicles

Athanasios G. Konstandopoulos, Souzana Lorentzou, Eleni Papaioannou, Georgia Kastrinaki & Dimitrios Zarvalis

Aerosol & Particle Technology Laboratory, CPERI/CERTH

JRC-CERTH Technical Meeting

CENTRE FORRESEARCH & TECHNOLOGY-HELLAS

CERTH

Functionalized Structured Reactors

Emission Control ReactorsSoot nanoparticles, CO, HC, NOx

Solar ReactorsThermochemical processesfor energy production

Functionalized Structured Reactor Development

Shaping of structured reactor bodies

(Nano)-Particle Synthesis

Coating/Functionalization of structured reactors

From Droplets to Particleswith Different Morphologies/Nanostructures

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

0.1 1 10

Droplet Size ( μ m )

Nor

mal

ized

Dis

tribu

tion

Size (µm)

10 nm10 nm10 nm10 nm10 nm

dropletsparticles

Aerosol Based Manufacturing Pilot Plant

synthesis

deposition

Ceramic Foam Fibrous metal Ceramic Honeycomb

Functionalized/Coated samples

Functionalizing/Coating Porous Supports

Flexibility in Deposition Mode

Inside the Pores LayerOn Surface

Inside Microchannels1.5 x 150 mm

Ash Accumulator: Aging performance

Nanoparticle Separation: Filtration & Pressure Drop

Reactor: Soot, CO/HC/NO oxidation, NOx reduction

Functions of an Emission Control Reactor (4WC)

Adding Multiple Catalytic Functions to a Porous Wall

Different Catalyst Particles

Separate CatalystFunctionalities

Catalyst 1Catalyst 2Catalyst 3

Substrate

High ΔP

Multi-Functional Particles

Low ΔP

Improvement in soot oxidation

0.0E+00

5.0E-04

1.0E-03

1.5E-03

2.0E-03

2.5E-03

250 300 350 400 450 500 550 600 650

Temperature (C)

1/m

0 (

dm

/d

t) (

s-1

)

Soot

Ce

CeZr

CeZrXY

CeZrX

CeZrXYZ

Wet Chemistry

0.0E+00

5.0E-04

1.0E-03

1.5E-03

2.0E-03

2.5E-03

250 300 350 400 450 500 550 600 650

Temperature (C)

1/m

o (

dm

/d

t) (

s-1

)

soot

CeCeZr

CeZrX

CeZrXY

CeZrXYZ

Aerosol Based

0

0.2

0.4

0.6

0.8

1

50 150 250 350

Temperature (C)

HC

co

nve

rsio

n

Material A

Material B

Material C

T50 < 140 C

NO to NO2 oxidation unaffected by HC

Material C

0

0.2

0.4

0.6

0.8

1

50 150 250 350 450 550

Temperature (C)

NO

co

nve

rsio

n

Eq.

wo HC

w HC

Equilibrium

w/o HC

w/ HC

200 ppm NO

100 ppm C2H4

10% O2 in N2commercialsample

HC oxidationat low temperature

Aerosol Synthesis of Diesel Emission Control Catalysts

Multi-Functional Filter-Reactor (MFR)

The MFR is a 4-way converter solution for soot nanoparticle removal and oxidation, CO and HC oxidation and NOx removal.

MFR Assessment

SAE 2009-01-0287

Our DPF samples 1, 2

0.0E+00

5.0E-04

1.0E-03

1.5E-03

2.0E-03

2.5E-03

3.0E-03

3.5E-03

4.0E-03

4.5E-03

300 350 400 450 500 550 600 650

Temperature (C)

1/m

(dm

/dt)

(s-

1)

State of the Art DPF

Uncoated

MFR1

MFR2MFR samples 1, 2

4 times higher soot oxidation rate at 550 C compared to a State of the Art DPF

“aged” “aged”

Doping for Thermal Resistance to Sintering

Mixed Oxide Catalyst MOC 1 Mixed Oxide Catalyst MOC 2

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

10 100 1000

dp (nm)

Filt

rati

on

Eff

icie

ncy

MOC2 aged

MOC2 fresh

MOC1 aged

MOC1 fresh

Size specific clean filtration efficiency

MFR Aging (equivalent to 100,000 km)

Aged Sample

New Samples

0.0000

0.0005

0.0010

0.0015

0.0020

0.0025

0.0030

0.0035

0.0040

0.0045

250 350 450 550 650

Temperature (C)

1/m

(dm

/dt)

(s-

1)

Fuel penalty comparison for different driving cycles

0.00%

1.00%

2.00%

3.00%

4.00%

5.00%

6.00%

NEDC Slow city cycle Interurban cycle Highway cycle

SA DPF

MFR

-45.2 % -18.4%

-17.1 %

-29.0 %

http://www.springer.com

Editors-In-Chief:Athanasios G. KonstandopoulosMansour Masoudi

‘Emission Control Science and Technology’ is the single, authoritative outlet for all areas of emission control research, development and application related to mobile (automotive-land/air/sea transport) and stationary sources in the energy, chemical process and manufacturing industries where combustion technologies are employed.

Functions of a Solar Thermochemical Reactor

Volumetric Receiver: Absorption of solar radiation/conversion into heat

Heterogeneous reactor: Gas solid reactions/Catalytic reactions

Key Enabling Technology: Redox Materials

2 2 x y

x y-δ 2 x y

2 x y1/2

H H + MM + C CO + M

Q +

O OO O O

O OM

Syngas (H2+CO)

Heat storagex y x y-δ 2M O + Q M O + /2O

Thermal reduction of oxide

Oxidation of reduced oxide

0

0.0005

0.001

0.0015

0.002

0.0025

0.003

0 20 40 60 80 100 120 140 160 180

Time (min)

H2 (

mm

ole

s/m

in/g

soli

d)

0

200

400

600

800

1000

1200

1400

Temp

erature ( oC

)

H2

T bed (C)

0

0.0005

0.001

0.0015

0.002

0.0025

0.003

0 20 40 60 80 100 120 140 160 180

Time (min)

CO

(m

mo

les/

min

/gso

lid)

0

200

400

600

800

1000

1200

1400

Temp

erature ( oC

)

CO

T bed (C)

0

0.0005

0.001

0.0015

0.002

0.0025

0.003

0 20 40 60 80 100 120 140 160 180

Time (min)

O2 (

mm

ole

s/m

in/g

soli

d)

0

200

400

600

800

1000

1200

1400

Temp

erature ( oC

)

O2

T bed (C)

Simultaneous H2O & CO2 splitting over a redox material

thermal reduction

CO2 splitting

H2O splitting

H2H2

CO

O2

CO

O2

Cycling ProcessReactant gas concentration: 100% CO2

0

0.005

0.01

0.015

0.02

0.025

0.03

0.035

0.04

2.6 4.6 6.6 8.6 10.6 12.6 14.6

Time (h)

CO

an

d O

2 c

on

cen

trat

ion

(mm

ole

s*m

in-1

*gre

do

x-1)

0

200

400

600

800

1000

1200

1400

1600

Tem

pe

rature

( oC)

CO O2 Temperature

2004 2005 2008 2011 2014

Solar Fuels Technology Evolution

2015

3 k

W, f

irst

pro

du

ctio

n o

f so

lar

H2

10

0kW

Χ 2

, pilo

t p

lan

t

3 k

W x

2, c

on

tin

uo

us

Η2

pro

du

ctio

n

1 M

W p

lan

t d

esig

n

HYDROSOL-I HYDROSOL-II HYDROSOL-3D HYDROSOL-PLANT

PROMETHEUS

75

0 k

W p

lan

t

1 M

W in

stal

lati

on

Advanced Grant

EXPO 2005 IPHE 2006 Descartes Prize 2007 EU IDEAS Award 2010 Taipei Inv. Tech. 2014

H2

H2O

O

CO2

COH2

H2O

O

CO2

COH2

H2O

O

Η2 + CO CxΗy (Liquid Fuels/Fischer-Tropsch process)

4Η2 + CO2 CΗ4 + 2H2O (Gas fuels, methane/Sabatier process)

Η2 + CO CxΗy (Plastics)

Sustainable Storage of Carbon AND Hydrogen!

Clean Energy & Materials from Sun, H2O & CO2

Solar Synthesis Gas

Solar Fuel Reactor

Multifunctional Emission Control Reactor

H2O

CO2

H2

CO

ICE

clean exhaust

O

O

O

C

C

HHredox

material

O

O

O

C O

O

C

C

HHredox

material

redox

material

CO, HC

NOx, Soot

Solar

O

O

O

C

C

HHredox

material

O

O

OO

C O

O

C

C

HHredox

material

redox

material

O

O

O

C O

O

C

C

HHredox

material

redox

material

redox

material

redox

material

redox

material

redox

materialO

O

C O

O

C

C

HHredox

material

redox

material

O

O

O

C O

O

C

C

HHredox

material

fuels

ICE

Vision: Sustainable Mobility and Clean Energy

CO2CO2

Air Capture

CO2

Enabler: Aerosol Based Manufacturing

20 nm

CO2

H2O

CH4, CxHyFuels & Chemicals

H2

Waste Heat for Solar Desalination H2O

Electric Energy

Clean Energy and Green Mobility

Carbon Neutral Solar Fuel Plant

Advanced Grant

EXPO 2005 IPHE 2006 Descartes Prize 2007 EU IDEAS Award 2010 Taipei Inv. Tech. 2014

Helionomics – Solar to Liquid (STL) Fuels

VEINS:CO2 pipelinesfrom Carbon Capture

ARTERIES:Carbon Neutral Solar Fuels Pipelines

CO2 producing Plants @ North

Solar Fuel Plants @ South

Biomimetic Integration of North and South

Processes/Treatment

Energy CarriersFood Raw Mat.

Transport /Distribution

Uses Impacts

Coal/LigniteNatural Gas

OilIndustrial MineralsWastes/PollutantsPlants and Animals

Solar EnergyOrganic &

AgriculturalResidues

Water

Hardware &Reactors

Control andSoftware

EconomicDevelopment

EnvironmentMankind

“SmartCommunities”

SustainableTechnologies

Supply Chains &Logistics

Networks /Pipelines

//

PROMETHEUS Energy Corridor: A Holistic Approach to Sustainability

RENEWABLES / LOW CARBON ENERGY SOURCES

ENERGY EFFICIENCY/EMISSION CONTROL

NOVELPRODUCTS & MARKETS

KNOWLEDGE CREATION & TRANSFER

EVIEX

HELPE RES

ENGAIA

EXELGROUP

APTLTHERMI

COMPUCON

SPANOS

ESTIA

DRAXIS

ITI, CPERI, HIT

ΣΠΑΝΟΣ ΤΕΧΝΟΛΟΓΙΕΣ ΙΚΕ

CHIMAR

CERTH

Clean Energy cluster

Regional Innovation and Smart Specialization

A Solar Thermochemical Proposal for the Black Sea’s life-threatening H2S

H2S produced at the bottom of the Black Sea is pumped disolved in water to a land station A

A HYDROSOL-like plant at B can convert H2S into H2

H2S S + H2 H2S + H2O SO2 + H2

H2S is separated at A and transferred to a sunny locationnearby e.g. Greece

2

1

3

Solar Cracking of H2S Solar Steam Reforming of H2S

Energy Corridor between Emirates-EU

CO2 export site

QATAR: Solar Fuel Production

Ship carries LNG from Qatar to EUShip brings from EU CO2 to Qatar

Acknowledgments

The European Commission for supporting our research in combustion engines and their emissions through >24 projects over the last 18 years including projects APT-STEP, CLEANER-D, HCV and our partners in these projects.

The European Commission for supporting our Hydrogen and Solar Fuels research with >16 projects including projects ARMOS, RESTRUCTURE, STORRE, NEMESIS2+, ARTIPHYCTION, BIOROBUR, EU-SOLARIS, HYDROSOL-3D and our partners in these projects

The Greek Secretariat for Research and Technology for supporting our research through projects HYDROSOL+ and NANOREDSOL.

Past and Current Industrial Partners including Molycorp, Tenneco, Ibiden, Honda, CR Fiat, AVL

Our colleagues at APTL

1996-2014

18YEARS