16.2.2016

Hannu Karjunen, LUTEero Inkeri, LUT

Tero Tynjälä, LUTPasi Vainikka, VTT

Eemeli Tsupari, VTTIlkka Hannula, VTT

Case St1: Identification of CO2 sources in Nordic Countries for PtX

SCOPE

• SITE LOCATIONS• CO2• INTEGRATION

• HEAT• OXYGEN

CO2 SOURCES• Steel mills• Cement and lime• Pulp mills• (CHP)• (Refineries)• Ethanol production• Chemical industry• Waste incineration• Biogas/WWTP

CO2 EmissionsReferences:• The European Pollutant Release and

Transfer Register (E-PRTR), 2007With partially updated values byVTT (up to year 2013)

• Finland: Energy authority emission data, 2014

• Sweden: The Swedish pollutant release and transfer register, 2014

• Individual site information (company’sannual environment reports, projectstudies etc.)

Steel mills

Applying carbon capture and storage to a chinese steel plant, Toshiba & Global CSS Institute.K. Onarheim et al. / International Journal of Greenhouse Gas Control 36 (2015) 93–105T. Kuramochi 88 et al. / Progress in Energy and Combustion Science 38 (2012) 87e112Arvola et al. / Low Carbon Economy, 2011, 2, 115-122

Carbon flow

• CO, CO2 flows• Possibilities for heat

integration• O2 needed in the

process, two puritylevels

• Challenge: not disturbing the existing process

• High annual operation hours (>8000)

Flue gas concentration CO2 CO

vol% vol%

Coke gas* 0 - 5 5

Hot stove gas 30

Blast furnace gas 20-25 20-25

Converter (Basic oxygen furnace) 16 60-70

Power plant 25-30

* 50-70% H2, 25-30% CH4

• FinlandSSAB, Raahe• Blast furnace• 3.8 Mt CO2

• Ship• Rail

SwedenSSAB, Luleå• Blast furnace• 1.2 Mt CO2

• Also other steel industriespresent, e.g. LKAB experimental blast furnace(CCS)

SSAB, Oxelösund• Blast furnace• 1.5 Mt CO2

Norway• Electric arc furnaces• Ferrosilicon production,

iron pellet production, smelters

• Biogenic component• Plants based on

hydropower integration, size smaller

• Some plants sellproduced CO, othersmay even use open flare*

Eramet, Sauda• 0.27 Mt CO2

• Ship

* ERAMET NORWAY SUSTAINABILITY REPORT 2014

FT Wax /a CO2 / a Electrolyser Gasoline

10 kt 44 kt 37 MW 140 GWh

1 MtCO2 = 3.2 TWhGASOLINE = 250 ktoe

Cement and lime

T. Kuramochi 88 et al. / Progress in Energy and Combustion Science 38 (2012) 87e112K. Onarheim et al. / International Journal of Greenhouse Gas Control 36 (2015) 93–105

CO2 concentration 15–22 vol%• Heat integration difficult

• usually no power plants or excess heat available/required on-site

• Flue gas contaminants(dust)

• Calcium looping• Oxyfuel combustion is

possible 27 €/tCO2 (Praxair)

Finland• Parainen0.62 Mt, ~30% recycled fuels• LappeenrantaFinnsementti, 0.37 Mt, ~40%

recycled fuelsNordkalk0.1 Mt(Fossil + biogenic)

Sweden• Degerhamn

0.26 Mt• Slite

1.7 Mt10 % of fuel is biomass

• Skövde• 0.35 Mt

Norway• ECRA oxyfuel pilot

project ongoing(norcem)

• Brevik• 30% Biomass• ~1.0 Mt

• Kjopsvik0.44 Mt

Lime production,fossil and biogenic.

https://www.globalccsinstitute.com/insights/authors/dennisvanpuyvelde/2013/09/20/capturing-co2-norwegian-cement-industry

Cement, fossil

Cement, biogenic

FT Wax /a CO2 / a Electrolyser Gasoline

10 kt 44 kt 37 MW 140 GWh

1 MtCO2 = 3.2 TWhGASOLINE = 250 ktoe

Pulp & Paper• Flue gas concentration (10-25vol%)• Flue gas contaminants• Biogenic and fossil component• CO2 capture cost 19 – 26 €/tCO2• Heat integration possible• Oxygen required by process

K. Onarheim et al. / International Journal of Greenhouse Gas Control 36 (2015) 93–105Gardarsdottir, S.O., Normann, F., Andersson, K., Johnson, F. 2014. Process evaluation ofCO2 capture in three industrial case studies. Energy Procedia, vol. 63, pp. 6565 – 6575.

Examples of production variation:

FinlandLappeenranta region cluster:Kaukas• 20 000 tO2/a by ASU• fossil CO2: 0.1 Mt• biogenic CO2: 1.5 Mt• BioVernoJoutseno, Imatra• Combined bio: 3.8 Mt

MtCO2 Fossil Biogenic Total

Finland 3.56 17.17 20.73

Sweden 1.22 22.39 23.61

Norway 0.03 0.32 0.35

Värö

Kaukas

Pulp & Paper

Ethanol production

• Ethanol fermentation sidestream is almost pure CO2 (~99%)

• 950 kg CO2 for 1000 kg of ethanol

• Biomass-derived syngas contains some impurities (H2S, hydrocarbons, nitrogen..) *

• Data to be verified with St1

C6H12O6 2 CO2 + 2 C2H5OH NorwayBorregaard• Fossil 0.17 Mt• Biog. 0.10 Mt• Biorefinery• Cellulosic

bioethanol• 528 m3/a

Larissa Noel, Pasi Vainikka, Carbon Balance Evaluation in Sugarcane Biorefineries in Brazil for Carbon Capture and Utilisation Purposes

SwedenLantmännenAgroetanol, Norrköping• 230 000 m3/a• 0.17 Mt

(high purityCO2)

FinlandSt1 Kajaani• Cellulosic

bioethanol• 10 000 m3/a• 7.5 kt (high

purity CO2)

* Energies 2013 6 3987-4000: A Two-Stage Continuous Fermentation System for Conversion of Syngas into Ethanol

Chemical Industry

• Fertilizers, olefins, polymers, silicon, rubbers…• Ammonia production has huge global potential

– 1500 TWh natural gas used annually for ammonia production

• CO2 separation already implemented for ammonia production• Hydrogen used already by existing processes

K. Onarheim et al. / International Journal of Greenhouse Gas Control 36 (2015) 93–105T. Kuramochi 88 et al. / Progress in Energy and Combustion Science 38 (2012) 87e112

FinlandBorealis Polymers Oy, Kilpilahti• Olefin production, 0.38 Mt• cracking and regeneration

units, process heaters and flares 0.54 Mt

SwedenBorealis krackeranläggning iStenungsund• 0.72 Mt CO2• Petrochemicals• Truck/Rail

NorwayYara, Porsgrunn• 0.72 Mt• Fertilizers• Ammonia plant, three nitric

acid plants, two NPK plants and two calcium nitrate (CN) plants

• Also petrochemicals nearby(~0.5 Mt)

Yara Uusikaupunki• Fertilizer processing, nitric acid

https://www.elkem.com/technology-and-innovation/our_technology_and_processes/

Carbon Capture and Storage in the Skagerrak/Kattegat region, 2012. http://www.ccs-skagerrakkattegat.eu/LinkClick.aspx?fileticket=OaxMXJOwfhY%3d&tabid=60

• High annual utilization• Biogenic component 40-60% of solid waste• MEA• Heat integration possible• Oxygen enrichment for low-grade fuels?

Waste incineration

Not a complete list. Data for Finland verified..

Waste-to-energy biogenic carbon dioxide reductions and USEPA’s Greenhouse gas reporting mandate – what does the future hold? http://www.ecomaine.org/education/NAWTEC%20Maritato%20Hewes%20paper.pdf

Biogas/WWTP• High CO2 content (30-40 vol%)• Small CO2 quantity

– Largest unit in Nordic countries: Viikinmäki, 8.8 kt

• Integration with biogas upgrading • Oxygen aeration• Methanol used in denitrification

Finland• 15 WWTP plants,11 solid waste treatment plants, 220 GWh• ~35 ktCO2/a total potentialSweden• 230 plants in Sweden: 1363 GWh

– 36 % was upgraded– ~180 ktCO2/a total potential

Location kt CO2/a

Helsinki, Viikinmäki 8.8

Espoo, Suomenoja 2.5

Jyväskylä, Nenäinniemi 1.3

Kuopio, Lehtomäki 0.63

Riihimäki 0.39

Forssa (solid waste) 3.1

Kouvola 1.1

Kokkola (solid waste) 0.2

QUESTIONS?

CHP• Lower load during the summer

– Still enough for PtX

• O2 integration: oxygen boosting / part load operation?

• Several sites available

• Unit scale: Kerava power plant: – 118 ktCO2/a, biomass– 21 MWe , 58 MWth– Solar panel field being installed (250 kW)

Example of yearly heating demand

condensing power plants are also visible on the mapnot complete, smaller plants missing

Refineries• Complex plants, limited space• Highly site-specific, various

products• Heat integration possible (fossil)• Hydrogen required for existing

processes• Oxygen integration possible if

heaters or boilers converted to oxy-fuel combustion

• Possibility: SMR replacement with electrolysis

K. Onarheim et al. / International Journal of Greenhouse Gas Control 36 (2015) 93–105CCS Roadmap for Industry: High-purity CO2 sourcesDet Norske Veritas. Global Technology Roadmap for CCS in Industry: Sectoral Assessment: Refineries

CO2 Emitter Description% of total refinery

emissions

Concentration of CO2 stream

Process Heaters

Heat required for the separation of liquid feed and to provide heat of reaction to refinery processes such as reforming and cracking

30-60 8-10

Utilities CO2 from the production of electricity and steam at a refinery. 20-50 4 (CHP Gas

turbine)

Fluid catalytic crackerProcess used to upgrade a low hydrogen feed to more valuable

products20-50 10-20

Hydrogen manufacturing

For numerous processes, refineries require hydrogen. Most refineries produce this hydrogen

on site. The requirements for Hydrogen increase with demands of stricter fuel quality regulation.

5-20 20-99

FinlandNeste Oil Porvoo• 2.8 Mt

SwedenGöteborg:• Preemraff Göteborg• St1 Refinery AB

Preemraff, Lysekil• 1.6 Mt

• CCS study done for theSkagerrak region (Lysekil, Preem, Yara and others)

NorwayGassco AS, Kårstø• 1.15 MtSTATOIL ASA, Mongstad• 1.6 Mt• CCS Projects

Hammerfest LNG• 1.6 Mt• Snøhvit CCS

Kårstø

Mongstad

LysekilSt1

Carbon Capture and Storage in the Skagerrak/Kattegat region, 2012. http://www.ccs-skagerrakkattegat.eu/LinkClick.aspx?fileticket=OaxMXJOwfhY%3d&tabid=60