Greenhouse Gas Plasma Chemistry: An Option for CO Control?€¦ · Poland Hungary USA -7. Bulgaria Estonia. EU. Latvia Liechtenstein Lithuania Monaco Rumania Switzerland Slovakia

UK-ISPC-18, Industrial Workshop 1

Greenhouse Gas Plasma Chemistry:

An Option for CO2 Control?

Ulrich Kogelschatz

Retired from ABB Corporate Research, Switzerland

Industrial Workshop on Plasma Chemistry18th International Symposium on Plasma Chemistry, Kyoto 2007


SouthpoleSipleD47 und D57 (Adelie Land)Mauna Loa, HawaiiDE08 and DSS (Antarctica)

260

280

300

320

340

360

900 1100 1300 1500 1700 1900 2100Year

Atm

osph

eric

CO

2C

once

ntra

tion

[ppm

]

Atmospheric Carbon Dioxide Concentration

Source: F. Joos, Europhysics News 27,1996, 213

辻野貴志

タイプライターテキスト

Copyright remains with the author(s).


Source: P. Brohan et al. J. Geophysical Research 111(2006), D12106


– Kyoto was a major watershed Climate Conference

– For the first time in history legally binding targets have been agreed upon for emissions from energy use

– A unique new experience in the global community

Kyoto 1997Kyoto 1997


Conditions: 55 parties and at least 55% CO2 1990 emissions

by UNFCCC Anex I parties

Entered into Force: February 16, 2005

December 2006: 169 countries and other governmental entities

(Still missing: USA, Australia)

The Kyoto Protocol of December 11, 1997


Kyoto Protocol 1997

0+1 Norway+1 Norway

+8 Australia+8 Australia

+10 Iceland+10 Iceland

0 UkraineNew ZealandRussia

0 UkraineNew ZealandRussia

--5 Croatia5 Croatia

--66 JapanJapanCanadaCanadaPolandPolandHungaryHungary

USAUSA --77

BulgariaBulgariaEstoniaEstonia

EUEULatviaLatvia

LiechtensteinLiechtensteinLithuaniaLithuania

MonacoMonacoRumaniaRumania

SwitzerlandSwitzerlandSlovakiaSlovakiaSloveniaSlovenia

Czech Rep.Czech Rep.--8%8%

Changes in GHG Emissions in 2008-2012 with Respect to Emissions in 1990

0


IPCC Report 2007

Global warming is realand very likely largely the result of human activities

To keep the temperature increase below 2 degrees C the world must stabilize atmospheric greenhouse

gases at 445 ppm by 2015(now approaching 400 ppm)


European Emissions Trading System (ETS)

CO2 emissions from large point sources(energy production, iron and steel, cement, glass, ceramics, paper and pulp). 11,400 installations emitting more than 2 billion tons of CO2 – nearly half of the carbon emitted in the EU.

Phase I (2005-2007) National Allocation Plans

Phase II (2008-2012) NAPs for 2008-2012

As from 2008, Member States may include additional installations/sectors as required and other GHGs(chemicals, aluminium and transport likely to be included).


Market Price of EU Allowances in EUR/t COMarket Price of EU Allowances in EUR/t CO22


Berlin Declaration – 50 Years European UnionMarch 25, 2007

”We intend jointly to lead the way

in energy policy and climate protection

and make our contribution

to averting the global threat of climate change”


European Goals (EU Council 8./9. March 2007)

Limiting the global average temperature increase to not more than 2°C above pre-industrial levels (IPCC Target)

is of vital importance

Commitment to a 30% reduction in emissions by 2020 below 1990 levels, in conjunction with other countries

(and by 20% in any event)

Binding target of 20% share of renewable energies by 2020

10% minumum target for the share of biofuelsin overall EU transport


Review on the Economics of Climate Change

Sir Nicolas Stern, former Chief Economist of the World BankOctober 30, 2006

Resource cost estimates suggest that an upper bound for the expected annual cost of emissions reductions consistent with

a trajectory leading to stabilisation at 550 ppm CO2e

is likely to be around 1% of GDP by 2050

We must act now !


Beyond KyotoEstablish World Wide GHG Trading System (CDM, JI)

Include the US, Australia, China, India

Develop low-carbon and high-efficiency technologies on an urgent timescale.

China stresses the importance of GHG trading systems

at Apec summit in Australia on August 3, 2007

Bush invites to a Climate Conference Sept. 27./28.2007The UN plans a conf. on Kyoto Successor on Bali Dec. 3. 2007


WorldWorld’’s Largest Energys Largest Energy--Related CORelated CO22 Emitters in 1994Emitters in 1994

Baldur Eliasson 1994Data: CDIAC, Oak Ridge National Laboratory

Total CO2 Emissions:6200 Million Metric Tons of C

1.4 %1.5 %1.6 %1.7 %1.8 %2.0 %2.4 %

3.3 %3.5 %3.8 %

4.9 %7.1 %

13.4 %22.4 %USA

ChinaRussiaJapan

IndiaGermany

ABB CustomersUK

CanadaUkraine

ItalyMexicoPolandFrance


CO2 Separation Unit at Shady Point, Oklahoma

1991200 t CO2/d

MEAScrubbing

Food-grade99.99%

Lummus


CCS Project at Sleipner Oil and Gas Field

Start 1996

1 Mio t/y

Picture: Statoil


Carbon Capture and Storage (CCS)Plans for Demonstration Plants (500 MW)

Kwinana, AustraliaBP and Rio Tinto

Carson, CA, USBP and EdisonMission Energy

Peterhead, ScotlandHydrogen Energy and

Scottish & Southern Energy


Vision of Baldur Eliasson

CO2


Reactor CO + H2LiquidFuels

CO2

CH4

GreenhouseGases Syngas FuelsEnergy

Greenhouse Gas ConversionGreenhouse Gas Conversion


DBD Reactor (1000 W, 30 kHz)

U. Kogelschatz et al. J. Phys. IV, France, 7(1997), C4-47 to C4-66

H2CO2CH4H2OO2

(Air)

Gas Inlet

DBD Reactor


Gas to Liquid Conversion via DBD PlasmaProduction of Liquid Fuel from a Methane/Carbon Dioxide Mixture

WaterWater--Methanol Heavy OilMethanol Heavy Oil Gasoline SampleGasoline SampleSample (CSample (C1212 -- CC2525)) (C(C33 -- CC1111))


Dominant Chemical Processes in CH4/CO2 Plasmas(DBD at atmospheric pressure)

K. V. Kozlov et al.Plasmas Polym.

5(2000), 129 - 150


DBD Plasma Reforming of CH4 / CO2 Mixtures

0

10

20

30

40

0 20 40 60 80 100C O 2 co n ten t in feed (%)

Syng

as a

mou

nt (m

ole)

0

1

2

3

4

H2/C

O ra

tio

H 2+C O

H 2/C O

U. Kogelschatz et al. GHGT-4, Interlaken 1998

H2 + CO

H2/CO


DBD Plasma Reforming of CH4 / CO2 Mixtures

U. Kogelschatz et al. GHGT-4, Interlaken 1998

0

20

40

60

80

0 200 400 600 800 1000T em p eratu re (°C )

Am

ount

(mol

e)

0 .0

0.5

1.0

1.5

2.0

H2/C

O ra

tio

H 2+CO

H 2/CO

E q u ilib riu m Calcu latio n :

M easu rem en t:

H 2/CO

H 2+CO

S im u latio n

Am

ount

(mol

%)

H2/C

O R

atio

Temperature (ºC)


DBD Plasma Reforming of CH4 / CO2 Mixtureswith NaX Zeolite Catalyst

B. Eliasson et al. Ind. Eng. Chem. Res. 39(2000), 1221-1227

80

60

40

20

00 20 40 60 80 100

CO2 Concentration in the Feed (%)

Con

vers

ion

(%)

CO2

CH4


Plasma Catalytic DBD Reforming of CH4 / CO2(Best Results with Zeolite HY)

K. Zhang et al. Ind. Eng. Chem Res. 41(2002), 1462

Selectivity toC4 Hydrocarbons

52%

(C4H8+ i-C4H10 + n-C4H10)

CH4

CO2

CH4/CO2 (molar ratio)

Con

vers

ion

(mol

%)


ConclusionsThe interaction of catalysts with non-equilibrium plasmas

requires further research

An intermediate goal might be, to generate syngas in the plasma and combine it with an advanced Fischer Tropsch synthesis to

produce synthetic fuels

Although plasma CO2 reforming of CH4 has not yet reached the energy efficiency of conventional reforming processes, there maybe

advantages in using small compact plasma reactors operating at low temperature and atmospheric pressure, e. g. for the processing

of stranded natural gas reserves in remote locations

Documents

Greenhouse Gas Plasma Chemistry: An Option for CO Control?€¦ · Poland Hungary USA -7. Bulgaria Estonia. EU. Latvia Liechtenstein Lithuania Monaco Rumania Switzerland Slovakia