the most important industrial sectors: lime&cement … · world lime production was 350 mt in...
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THE MOST IMPORTANT INDUSTRIAL
SECTORS: LIME&CEMENT AND
IRON&STEEL
24-25.1.20177th RESEARCHERS’ SEMINAR
Eemeli Tsupari, VTTMarkus Hurskainen, VTT
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Why focus on cement/lime and steel?Industrial Direct CO2 Emissions by Sector, 2007
• PV and wind power are ”easy” solutions to decarbonise the powersector
• The challenge is in industrial emissions and transportation
• Globally >50% of industrial CO2emitted from two sectors
• Often said that CCS is the only option• This is NOT true!
Data: IEA Energy technology perspectives 2010Fig: Reducing CO2 emissions from heavy industry 2012
Cement 26%
Iron & steel30%
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1. LIME
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How is lime made?
CaCO3 + heat CaO + CO2Typically at 900-1200°C Heat provided by direct contact with hot flue gases
Theoretical heat demand 3.18 GJ/t of quicklime (CaO)
EU average 4.25 GJ/t CaO
Fig: EuLA. A Competitive and Efficient Lime Industry – Summary
JRC (2013). BAT BREF
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World lime production was 350 Mt in 2015
- China produces ~2/3 of the total lime
- The EU ~20 Mt (6% of total)
- Production has increased only slightlyduring last 10 years
Sources: International Lime Association (ILA) & U.S. Geological Survey& EuLA Activity Report 2015
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CO2 emissions from limekilns globally
The estimated CO2 emissions from lime production are around 450 Mt/a.• This corresponds to ~1.2% of total
man-made CO2 emissions.
• ..or around 10 times the annual CO2emissions from the energy & industry sectors in Finland.
Around two thirds of CO2 originatefrom limestone
Fig: EuLA. A Competitive and Efficient Lime Industry – Summary
Distribution of CO2 emissions from lime kilns in the EU
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Fuels used in lime kilns in the EU in 2010
Total fuel use ~90 PJ (25 TWh)(assuming 4.25 GJ/t CaO and 21 Mt/a lime production)
In China, coal is by far the most used fuel.
Source: EuLA. A Competitive and Efficient Lime Industry – Summary
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Sources of information
European Lime Association, http://www.eula.eu/EuLA (2014). A Competitive and Efficient Lime Industry - Technical report by Ecofys, http://www.eula.eu/file/477/download?token=G4HAme1uEuLA (201x). A Competitive and Efficient Lime Industry – Summary, http://www.eula.eu/file/475/download?token=5lpX8a3hEuLA (2016). Activity Report 2015-2016, http://www.eula.eu/file/581/download?token=H1P7f8uh
International Lime Association (ILA) http://www.internationallime.org/home/
U.S. Geological Survey lime production statistics https://minerals.usgs.gov/minerals/pubs/commodity/lime/index.html#myb
JRC (2013). Best Available Techniques (BAT) Reference Document for the Production of Cement, Lime and Magnesium Oxide, http://eippcb.jrc.ec.europa.eu/reference/BREF/CLM_Published_def.pdf
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2. CEMENT
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Production of cement
The main raw materials for cement are limestone, sand, clay, (ashes)
1. Decomposition of CaCO3 at about 900 °C to CaO and CO2
2. Clinkering process in which the calcium oxide reacts at~1 400–1 500°C with sand and clay to form the silicates, aluminates, and ferrites of calcium
3. The clinker is then cooled rapidly, ground or milled together with gypsum and other additives to obtain cement.
Composition of grey cement
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Total world cement production 4 600 Mt in 2015
Source CEMBUREAU (2016). Activity Report 2015.
• Total production one magnitude higher than lime
• Rapid increase in developing countries
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CO2 emissions from cement production
• Ca. 55% of the emissions are process emissions (from CaCO3), 35% comes from the burning of the fuels to heat the kiln, and ca. 10% comes from electricity use and transportation.
• The total CO2 emissions are estimated to be around ~3 Gt/a, which equals to ~8% of total man-made emissions.• By extrapolating from the CSI GNR data* (which covers 21% of world’s cement
production)
55%35%
10%
CO2 emissions from cement production
Process
Fuel
Electricity
Sources: *Cement Sustainability Initiative - Getting Numbers Right databasehttp://www.wbcsdcement.org/GNR-2014/index.html
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Fuels used in cement kilns in 2012 (and prediction for 2025)
• Coal is the most common fuel especially in non-OECD countries• Share of bio/waste fuels is expected to increase
Source: IEA Tracking Clean Energy Progress 2015
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Sources of information
The European Cement Association (CEMBUREAU) http://www.cembureau.be/
CEMBUREAU (2016). Activity Report 2015, http://www.cembureau.eu/2015-activity-report
CEMBUREAU (2013).The role of cement in the 2050 low carbon economy, http://lowcarboneconomy.cembureau.eu/uploads/Modules/Documents/cembureau-brochure.pdf
CEMBUREAU (201x). Cement for low-carbon Europe through clinker substitution http://www.cembureau.be/sites/default/files/documents/Cement%20for%20low-carbon%20Europe%20through%20clinker%20substitution.pdf
The Cement Sustainability Initiative, http://www.wbcsdcement.org/index.php
”Getting numbers right” http://www.wbcsdcement.org/GNR-2014/index.html (Statistics)
JRC (2013). Best Available Techniques (BAT) Reference Document for the Production of Cement, Lime and Magnesium Oxide, http://eippcb.jrc.ec.europa.eu/reference/BREF/CLM_Published_def.pdf
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NEOCARBON SOLUTIONFOR LIME & CEMENT?
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Calcination by renewable electricity
• Indirectly heated calciner using electrical heaters:Replacement of fossil fuels by renewable electricity
• Avoidance of fuel based CO2
• Potential business case if expensive fuels (e.g. oil) are replacedProduction of pure CO2 from CaCO3
• Magnitude ~ 2 times the CO2 needed for aviation fuelsCaO not contaminated by combustion by-products
• Main research questions:– Heat transfer in large scale– End product properties (particle size, reactivity…)– Heat integration
CaCO3
CaO
Pure CO2
Electrical heaters
Heat transfer
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Experiments at VTT (CCSP 2016)
• Successful pre-calcination of lime mud (from pulp mill)• Production of 95%..98% pure (biogenic) CO2
• Next: Funding for CFD studies and scale-up
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Project LEILAC - Low Emission Intensity Lime and Cement project (Horizon 2020)
• Aims to developed indirectly heated calciner for lime/cement industry
– Pure CO2 stream (possibly with H2O)
• Project commenced on the 1st January 2016 and will run for five years
• HeidelbergCement, Lhoist, Cemex, Tarmac, Calix, AmecFW, ECN…
Should be possible to develop similar indirectly heated calciner using electrical heaters also?
http://www.project-leilac.eu/
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IRON AND STEEL
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Main processes• Over 99% of global steel production by two process routes
• ~60% by Blast Furnace and Basic Oxygen Furnace (BF+BOF) route• ~40% by Electric Arc Furnace (EAF) route
• EAF route is less C-intensive but limited by the scrap availability• Approximately >80% of CO2 steel sector from BF+BOF• Also EAF processes are significant CO2 sources
Original figure: http://www.worldcoal.org/coal/uses-of-coal/coal-steel/
a.k.a. OBC (Oxygen BlownConverter)
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So far, focus on BF processcase example: SSAB’s Raahe steel mill – the largest CO2 point source
in Finland
Original figure: http://www.worldcoal.org/coal/uses-of-coal/coal-steel/
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CO2 emissions
Original figure: http://www.worldcoal.org/coal/uses-of-coal/coal-steel/
Power plant
(60% .. ) >70% of CO2 emissions
Hot stoves(a.k.a. ”Cowpers”)
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Process gases
Original figure: http://www.worldcoal.org/coal/uses-of-coal/coal-steel/
Power plant
Coke oven gas
Converter gasBF gas
Hot stoves(a.k.a. ”Cowpers”)
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Process gases are attractive for synthesis
Source: Arasto, Tsupari, Kärki, Lilja, Sihvonen. Oxygen blast furnace with CO2 capture and storage at an integrated steel mill - Part I: Technical concept analysis. International Journal of Greenhouse Gas Control. Volume 30, November 2014, Pages 140–147
MeOH/electricity = 77%!(56% with CO2 solely)
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25.1.2017 25
Research for large CO2 reductions
www.neocarbonenergy.fi
https://www.sintef.no/globalassets/sintef-energi/nordiccs/d4.2.1501-d18-co2-capture-cases.pdf
http://www.vtt.fi/inf/pdf/science/2015/S111.pdf
https://www.fimecc.com/programs/simp
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The options studied in other projects
Original figure: http://www.worldcoal.org/coal/uses-of-coal/coal-steel/
Power plant
(60% .. ) >70% of CO2 emissions
PC CCS
VPSA
CO2 transport and storage
Biomass
GTCCPre-comb.
capture
Case 1: ”PC CCS”Case 2: ”OBF” *
Case 3: ”OBF+CCS”Case 4: ”GTCC”
Case 5: ”GTCC+CCS”Case 6: ”Biomass”
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STEEL MILL STUDIES IN NEOCARBON
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Original figure: http://www.worldcoal.org/coal/uses-of-coal/coal-steel/
Electrolysis
O2 utilisationneed for high purity O2in BOF• O2 consumed also in BF
Synthesis
Process gases including H2 and COCoke oven gas & converter gas(also blast furnace gas, if upgraded)
Steam to mill’ssteam network
SNG /methanol /gasoline /ethanol
H2
Power-to-fuels from converter gas
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10% PCC + PtMeOH
Original figure: http://www.worldcoal.org/coal/uses-of-coal/coal-steel/
Power plant
Steam
PCC PtX
O2
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Resultsdefault valuesCO2
€/t80 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##77 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##74 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##71 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##68 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##65 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##62 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##59 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##56 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##53 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##50 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##47 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##44 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##41 ## ## ## ## ## ## ## ## ## ## ## -9 -6 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -6 -6 -6 -6 -7 -7 -8 -9 ## ## ## ## ##38 ## ## ## ## ## ## ## ## ## ## -7 -4 -2 -2 -1 -1 -1 0 0 0 -1 -2 -2 -3 -4 -5 -6 -7 -7 -8 -9 ## ## ## ## ##35 ## ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -1 -1 -1 0 0 0 -1 -2 -2 -3 -4 -5 -6 -7 -7 -8 -9 ## ## ## ## ##32 ## ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -1 -1 -1 0 0 0 -1 -2 -2 -3 -4 -5 -6 -7 -7 -8 -9 ## ## ## ## ##29 ## ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -1 -1 -1 0 0 0 -1 -2 -2 -3 -4 -5 -6 -7 -7 -8 -9 ## ## ## ## ##26 ## ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -1 -1 -1 0 0 0 -1 -2 -2 -3 -4 -5 -6 -7 -7 -8 -9 ## ## ## ## ##23 ## ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -1 -1 -1 0 0 0 -1 -2 -2 -3 -4 -5 -6 -7 -7 -8 -9 ## ## ## ## ##20 ## ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -1 -1 -1 0 0 0 -1 -2 -2 -3 -4 -5 -6 -7 -7 -8 -9 ## ## ## ## ##17 ## ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -1 -1 -1 0 0 0 -1 -2 -2 -3 -4 -5 -6 -7 -7 -8 -9 ## ## ## ## ##14 ## ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -1 -1 -1 0 0 0 -1 -2 -2 -3 -4 -5 -6 -7 -7 -8 -9 ## ## ## ## ##11 ## ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -1 -1 -1 0 0 0 -1 -2 -2 -3 -4 -5 -6 -7 -7 -8 -9 ## ## ## ## ##
8 ## ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -1 -1 -1 0 0 0 -1 -2 -2 -3 -4 -5 -6 -7 -7 -8 -9 ## ## ## ## ##5 ## ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -1 -1 -1 0 0 0 -1 -2 -2 -3 -4 -5 -6 -7 -7 -8 -9 ## ## ## ## ##
10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80Sähkön hinta (sis. siirto ja netto verot), €/MWh
10%PCC+MeOH
OBF+CCS
OBF
PtMeOH fromconverter gas
GTCC+CCS
GTCC
Reference
Note: Long term study. Some improvements to Raahe steelmill’s existing process are assumed also for the reference case
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CO2€/t
80 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##77 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##74 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##71 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##68 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##65 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##62 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##59 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##56 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##53 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## -8 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##50 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## -7 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##47 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## -9 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##44 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## -8 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##41 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## -9 -6 -4 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##38 ## ## ## ## ## ## ## ## ## ## ## ## ## ## -8 -5 -3 -4 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##35 ## ## ## ## ## ## ## ## ## ## ## ## ## -7 -4 -2 -3 -4 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##32 ## ## ## ## ## ## ## ## ## ## ## -9 -6 -3 -1 -2 -3 -4 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##29 ## ## ## ## ## ## ## ## ## ## -8 -5 -2 -2 -1 -2 -3 -4 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##26 ## ## ## ## ## ## ## ## ## -7 -4 -2 -2 -2 -1 -2 -3 -4 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##23 ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -2 -1 -2 -3 -4 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##20 ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -2 -1 -2 -3 -4 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##17 ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -2 -1 -2 -3 -4 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##14 ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -2 -1 -2 -3 -4 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##11 ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -2 -1 -2 -3 -4 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##
8 ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -2 -1 -2 -3 -4 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##5 ## ## ## ## ## ## ## ## -9 -6 -2 -2 -2 -2 -1 -2 -3 -4 -5 -6 -6 -7 -8 -9 ## ## ## ## ## ## ## ## ## ## ## ##
10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80Sähkön hinta (sis. siirto ja netto verot), €/MWh
Resultshigher coke price and CO2 trans.&stor.cost
10%PCC+MeOH
OBF+CCS
OBF
PtMeOH fromconverter gas
GTCC+CCS
GTCC
Note: Long term study. Some improvements to Raahe steelmill’s existing process are assumed also for the reference case
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NEXT
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CO2 free steel mill
http://carbonmarketwatch.org/wp-content/uploads/2016/04/SSAB-HYBRIT-A-Swedish-prefeasibility-study-project-for-hydrogen-based-CO2-free-ironmaking.pdf
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Discussion and conclusions
• Lime, cement and steel are the most important industrial sectors in terms of global CO2 emissions
• Limestone calcination reaction can be directly electrified
• There are several attractive integration opportunities for PtX processes with different steel making processes
– High efficiency with converter gases– In addition, direct reduction by hydrogen is possible!