Carbon Dioxide Utilization (CDU) · • CDU is an essential part of the CC portfolio that includes...

Bringing people interested in CO2 utilization togetherBringing people interested in CO2 utilization together

Carbon Dioxide Utilization (CDU):

Peter StyringChemical & Biological Engineering, The University

of Sheffield, UK

Acknowledgements

• Katy Armstrong

• Dr Somsak Supasitmongkol

• Dr Ortrud Aschenbrenner

• Andrew Gill

• Royal Thai Government and National Metal and Materials Technology Center (MTEC)

• EPSRC “C-Cycle Consortium” (EP/E010318/1)

• EPSRC CO2Chem Grand Challenge Network

Bringing people interested in CO2 utilization together2


CO2Chem Overview

The Energy Question

Product Landscape

Conclusions

Capture Agents

Carbon Capture and

Utilisation in the

green economyUsing CO2 to manufacture fuel, chemicals and materials

Authors

Peter Styring (The University of

Sheffield), Daan Jansen (ECN)

Co-authors

Heleen de Coninck (ECN), Hans

Reith (ECN),

Katy Armstrong (The University

of Sheffield)

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Key Research Priorities

Hydrocarbons


CDU in CO2Chem


EconomicViability

• CCS: Point Source Capture /

• Remote Storage / No Utilisation /

• Techno-economic Loss, Socio-economic Gain

• EOR: Point Source Capture / Remote Storage/ Crude Oil into Supply Chain / Economic Gain

• CDU: Point Source Capture / Local Storage / Diverse Chemical Production / Economic Gain

• Long-term need for air capture and local production with local energy integration


Bringing people interested in CO2 utilization together

Styring, Dowson & Armstrong, The Catalyst Review, 2013

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http://www.olicognography.org/graph/energydensity.jpg


Alternative Energy Sources • Solar Intermittent, geographical

• Wind Intermittent

• Tidal Predictable, geographical

• Hydro Geographical

• Nuclear Political, constant output

• Geothermal Geographical

The commonality between all these renewable sectors is the production of electricity, or simply a supply of electrons.

Bio- and crop-based renewables are not included above but examples include maize, sugar beet and algae


Washington DC2013

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North of England1973

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Range?Battery to Vehicle weight ratio?Recharge time?Recharge availability?Life Cycle Assessment?

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Efficiency20% Current

33% max. single junction

Efficiency59% max

Efficiency70%

Transport to Grid

Efficiency80% max

Solar Wind Tidal

Limited storage capacity

Efficiency70%

41% max 56% max

14% current23 % max

How can CDU help in renewable intermittent energy storage?

• Buffering intermittent power generation.

• Converting electrical to chemical energy which is easier to store.

• Can convert to liquid or gas. Liquids tend to have higher energy densities.

• Offers alternatives to distributed power, including remote, local conversion.

• Easier storage and transport solutions.

• Value-added product from a renewable resource.


Polymers

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A Coordinated, Comprehensive approach to Carbon Capture and Utilisation

• Consortium of four UK universities: Sheffield, UCL, Queens Belfast, Manchester

• £7.5 M

• 9 Post-doctoral positions and Project Manager

• Four year programme of research

• Whole System approach:– Life Cycle Analysis

– Carbon Capture Reagents, ionic liquids & polymers

– Flue Gas & AD Off-gas conversion

– Fuels from CO2

– Molecular Modelling


4CU

• 4 year, £5.7m project funded by EPSRC started September 2012

– University of Sheffield

– University College London

– Queens’ University Belfast

– Manchester University

• Steering committee of industrialists and academics

• Consider two industrially important types of gas stream containing CO2:

– Flue gas

– CH4/CO2

• Produce Fuel

• All experimental and modelling work evaluated using process analysis and life cycle analysis

• Selected anaerobic digestion of wet waste as an example process

SP3 & SP4SP5 & SP6

SP7


Capture

Capture Capture Agents• Adsorption vs Absorption

• Chemisorption vs Physisorption

• Liquid sorbents vs solid sorbents

• Amine sorbents

– MEA, DEA, MDEA

• Ether sorbents

– Selexol, Rectisol

• Chilled ammonia

• Membranes

• MOFs and zeolites

• Ionic liquids & Ionic Polymers

• Activated carbons


PILmonomer


Ionic Liquid-Gas Adsorption


Substance Maximum Adsorption

Capacity, % (w/w)

Adsorption Energy,

kJ mol-1

[C2mim][ES] 1.70 –27.89

[C2mim][Tf2N] 3.67 –16.56

[C4mim][Tf2N] 3.45 –16.19

[C4mpy][Tf2N] 3.40 –23.35

[C6mpy][Tf2N] 3.23 –21.62

[C6mim][OTf] 4.09 –19.00

[P66614][Tf2N] 2.90 –15.90

[VBTMA][PF6] 1.10 –24.60

P[[VBTMA][PF6]] 2.50 –19.52

Substance Maximum Adsorption Capacity,

% (w/w) by TGA

Maximum Absorption

Capacity, % (w/w)

[C2mim][ES] 1.70 12.00

[VBTMA][PF6] 1.10 47.25

P[[VBTMA][PF6]] 2.50 77.46

CO2 capacity by weight and adsorption energy in a fluidized bed absorber at atmospheric pressure

CO2 capacity by weight and adsorption energy for ionic liquids determined by TGA at atmospheric pressure


Ionic Liquids

Solubility of various gases in 1-hexyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imideSanchez, L.M.G., 2008. Functionalized Ionic Liquids: Absorption Solvents for Carbon Dioxide and Olefin Separation. Gildeprint: The Netherlands.

[C2mim][ES] by TGA


PIL by TGA


Release

• Lower energy than amines

• IL monomer shows slow release (blue)

• PIL (red) releases CO2

rapidly

• Reduces plant dimensions

• Negligible evaporative loss for PIL

• Relatively low operating costs (Design Projects) but high materials cost in CAPEX


ILm & PIL


• PIL white porous solid with excellent performance but at a

cost. Approximately 1500 times more expensive than MEA but more stable with smaller plant requirements.

• ionic liquid IL1 white solid. Easily synthesised at low

cost. Robust with low vapour pressure. Cost comparable to MEA and more stable with smaller plant requirements.

• ionic liquid IL2 white solid. Easily synthesised at slightly

higher cost than IL1 as it contains additional fluorine atoms in the anion. Robust with low vapour pressure.

Sorbents Costs


0

2

4

6

8

10

12

14

16

18

0 10 20 30 40 50 60 70 80 90 100

Ab

sorp

tio

n C

apac

ity,

%(w

/w)

Temperature, oC

IL1 (H)

IL2 (F)

Temperature dependence of sorbents


optimum desorption T

optimum desorption T

T swing = 30 oC

T swing = 20 oCoptimum absorption T

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0

2

4

6

8

10

12

14

16

18

0 5 10 15 20 25 30 35 40 45

Ab

sorp

tio

n C

apac

ity,

%(w

/w)

Time, min

IL1 (H)

IL2 (F)

Uptake kinetics of sorbents



CDU Product Landscapes


Cyclic Carbonates


Entry Catalyst (mol%) Co-catalyst

(mol%)

Temp (oC) Conversiona

(%)

1 AlCl(salenac)OH (1.0) - 25 0

2 AlCl(salenac)OH (2.5) Bu4NBr (2.5) 25 0







9 - Bu4NBr (1.0) 110 70

Reaction conditions: AlCl(salenac)OH (1-2.5 mol%); Bu4NBr (1-2.5 mol%); styrene oxide (2 mmol),CO2 1 bar and co-solvent (DCM) 5 ml for 48 hr. aConversions were calculated from GC analysis databased on styrene oxide by using tetradecane as internal standard.

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Conclusions

Conclusions


• CDU is an essential part of the CC portfolio that includes CCS, EOR and EGR. It will produce profit and have socio-economic benefits if the Publics are engaged and informed.

• Integration of with renewable intermittent energy sources offers energy storage and security as well as the possibility for remote local fuel production.

• Air capture will become increasingly important so needs to be addressed now.

• An comprehensive approach using multiple technologies is required and this must include sensible Life Cycle Assessments.

• CO2Chem is aiming to move the political and scientific landscape in the UK and Europe.

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Carbon Dioxide Utilization (CDU) · • CDU is an essential part of the CC portfolio that includes...

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