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Mineralisation of CO2 using serpentinite rock -
towards industrial application
Ron Zevenhoven and co-workers; presented by Mikko Helle Åbo Akademi University, Turku, Finland
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 1
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Overview
Finland’s Cleen CCS Program 2011-2015 – CCS / CCU / CCUS in Finland
The ÅA route for stepwise serpentinite carbonation – Mg(OH)2 production from magnesium silicate-based rock – Mg(OH)2 carbonation – Process energy use – Large-scale application; direct operation on flue gas – Alternative reaction intermediates for Mg(OH)2
Conclusions
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 2
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Research areas Cleen Oy CCSP 17 industrial + 9 research partners, 1.1.2011 – 31.12.2015, ~ 5 x 3 M€
1. CCS concepts – CHP (Combined Heat and
Power) – Other industries – Bio-CCS
2. Capture solutions – Oxy-fuel combustion – Looping technologies – Post-combustion capture – Emission measurements
3. Transport of CO2 and intermediate storages
4. Storage solutions – CO2 storage capacity assesment
of the Baltic Sea – Storage monitoring – Mineralisation
5. New ways to utilize CO2
– Algae cultivation
– Fuel components – Precipitated calcium carbonate
6. Regulatory complience, acceptability of CCS and other common aspects
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 3
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CO2 storage capacity assessment of the Baltic Sea
Research collaboration with the Swedish CCS project (Bastor2) A first estimate on the geological storage potential of CO2 in the Baltic Sea
has been made: 16 Gt theoretical capacity
Existing geological data from oil exploration and geological maps were used for assessing the potential
Report now available: http://www.vtt.fi/inf/pdf/technology/2013/T101.pdf
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 4
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CCUS / CCS in / for Finland
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 5
In Finland Near Finland / abroad
Geological storage Not possible Baltic sea ?
Ocean storage Not possible Not possible
Mineral sequestration Large potential Projects ongoing
Projects ongoing PT, SG, LT, (CA?, ZA?)
CO2 utilisation Several applications (PCC, CO2 solvent...) Projects ongoing
Projects ongoing US
earlier:
”CCS”
”CCU”
* Carbon capture, utilisation and storage, or Carbon capture, use and sequestration
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CO2 mineralization: what, how
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 6
IPCC SRCCS
2005 Chapter 7
Overall carbonation chemistry, with M = Mg or Ca (or Fe, ...) MO.ySiO2.zH2O (s) + CO2 (g) < = > MCO3 (s) + ySiO2 (s) + zH2O (l) + HEAT
Process energy
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CO2 mineralization potential Much larger potential
than other CCUS options, for example:
Olivine-containing rock in Oman (350 × 40 x 5 km, ~30% olivine)
Could bind all fossil carbon
Available world-wide, hence increasing attention
No ”leakage” problems from carbonates
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 7
Lackner, Science vol. 300, 2003, 1677-1678
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CO2 mineralization potential: Oman
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 8
Pictures: R Hunwick Presented in Sydney, March 12, 2012
Olivine-containing rock in Oman (350 × 40 x 5 km, ~30% olivine) Kelemen & Matter, PNAS 2008)
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CO2 mineralisation in Finland For Finland the only CCS option in or
close to the country is CO2 mineral sequestration, at least 2-3 Gt capacity
Interest so far limited mainly to metal / limestone / mineral processing sector
Producing valuable solids is one economic driver
Cooperation with countries in a similar situation: Singapore, Portugal, Lithuania (South-Africa)
”Capture” appears to make CCS too expensive operate on flue gases directly!
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 9
Meri-Pori power plant (2.5 Mt CO2/y)
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MgSO4 etc.
Magnesium silicate mineral (e.g. serpentinite)
CO2 (pure or flue gas)
Iron oxide (→ iron/steel industry)
Ammoniumsulphate recovery
Mg(OH)2
Steam
MgCO3
HEAT
NH3 + H2O
AS
Pressurised fluidised bed
> 20 bar, > 500°C
AS + Mg-silicate reactor
Magnesium- (and iron) extraction
AS
Mg-extraction Mg(OH)2 production MgCO3 production
SiO2 + unreacted
Mg-silicate carbonation: the ÅA route
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 10
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Closed loop process producing Mg(OH)2 from Mg-silicate rock
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 11
Nduagu, dr. thesis ÅA 2012
Specific surface 40 – 50 m2/g Pore volume 20 – 25 cc/g
pH ~
8.5
pH ~
11.5
Oven chamber
Reactor 3
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Mg(OH)2 carbonation @ ÅA 2007: the fluidised bed set-up
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 12
PPdif
3 m
2 m
CO2
T
SAMPLEFEED
CO2 OUT P
FLU
IDIS
ED
BE
D
PRE-HEATER
CYCLONE
ΔP-GAUGE
H2OFILTER
T
T
T
T
T
FLOW-METER
H2O
SAMPLE COLLECTING
Preheater Research questions: 1) No build-up of MgCO3 on Mg(OH)2 particles?, 2) Fast kinetics? 3) What about supercritical CO2?
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0.00
0.20
0.40
0.60
0.80
1.00
470 480 490 500 510 520 530 540 550 560
Com
posi
tion
(%
-wt)
Temperature (°C)
MgO
MgCO3
Mg(OH)2
unusually high Mg(OH)2
Mg(OH)2 carbonation – results using Dead Sea Periclase material (BET ~ 5 - 8 m2/g)
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 13
~ 20 bar CO2 → ~ 58 bar CO2
Fagerlund 2009, 2010
scCO2: no
advantage (tests up to
~80 bar)
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PFB carbonation of Mg(OH)2
Competition between dehydroxylation and carbonation – Improve precipiation conditions, control Mg(OH)2 properties – Circulating PFB would allow for finer particles ?!
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 14
Fagerlund, dr. thesis ÅA 2012
Most tests with Dead Sea Periclase
x
x Mg(OH)2 from Portuguese serpentinite (Bragança) June 2013
~ 45 m2/g
T: up to ~ 600°C pCO2: up to 80 bar
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Process energy use
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 15
Mechanical vapour recompression (MVR) crystallization for AS salt recovery
MVR compression work ~1.2 GJ/t CO2
-100-50
050
100150200250300
0 200 400 600 800 1000Rea
ctio
n en
thal
py Δ
H (k
J/m
ol)
Temperature (°C)
Reaction Enthalpies
Mg(OH)2 + CO2Serpentine + ASSerpentinite rock + AS
Reaction enthalpies vs. temperature for extraction of 1 mol of Mg from pure
serpentine or from Finnish serpentinite, and for the carbonation .
Mg(OH)2 production needs 3 - 4x the heat
the carbonation gives
Total penalty for a stand-alone process : ~3 GJ (mainly 400°C heat) and ~3 t rock per ton (1000 kg) CO2
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Progress towards >90% conversion
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 16
50% 90% 100% 100% 90% 50%
Mg extraction from rock 100%
Carbonation of extracted Mg
9/2013
3/2012
1/2010
4/2007
8/2008
6/2009
Next challenge: >> 90% recovery of ammonium sulphate salt
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Conversion of Mg(OH)2 to MgCO3 and MgO in (wet) CO2 or CO2 diluted with (26-72%) N2.
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 17
Total pressure 10 – 59 bar, temperature 450 - 550°C, time 15 minutes Dead Sea Periclase (DSP) Mg(OH)2, 212-425 µm
0.00
0.20
0.40
0.60
0.80
1.00
0.000.200.400.600.801.00
MgO
-con
tent
Mg(OH)2-content
No nitrogen
Added nitrogen
0.00
0.20
0.40
0.60
0.80
1.00
0.000.200.400.600.801.00
MgC
O3-
cont
ent
Mg(OH)2-content
No nitrogen
Added nitrogen
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Application at a lime kiln ~ 200 kg CO2 / h
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Challenge: Diopside
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Mg-silicate carbonation at a lime kiln
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18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 20
Kiln flue gas
Exit gas
AS
Rock
MgCO3
Hot water DH system
Rest water
water AS FeOOH
wet NH3
water
Mg-silicate carbonation at a lime kiln
Slotte et al. ENERGY 2013
Integration at an industrial lime kiln, no CO2 capture,
full flue gas compression to 80 bar ~ 20 bar CO2, 0.2~0.25 t CO2/h fixed,
heat (kiln gas) 2.6 GJ/t, power 0.9 GJ/t CO2
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Alternative route: MgSO4 carbonation in aqueous solution /1
+: No need to produce and carbonate Mg(OH)2
+: No CO2 capture stage, no NH3 injection in flue gas duct - : No carbonation heat can be recovered - : Product is hydromagnesite ~ only 4/5 of Mg carbonated
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Alternative route: MgSO4 carbonation in aqueous solution /2
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 22
Extracted (Mg,Fe)SO4 solution from serpentinite pH = 2.05
+VNH4OH pH ~ 8.5 → Iron precipitation → 60 min → Filter
MgSO4 solution +VCO2 pH ~ 6
+VNH4OH pH ~ 10 → Hydromagnesite precipitation → 60 min → Filter
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Alternative route: MgSO4 carbonation in aqueous solution /3
Iron (hydroxy) oxide and hydromagnesite can be
precipitated separately or not
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 23
N22 l/min
NH3
H2ON2
(SO2)
T = 440 °C
AS + S Mg2+ Fe2+ SO42-
CO2
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Conclusions CO2 mineral sequestration offers a leakage-free alternative for
CO2 underground storage worldwide; only option in Finland CO2 capture from oxygen containing gases isn’t ”taking off”, and
capture is more expensive than economically viable CC(U)S! no capture step, operate mineralisation directly on flue gas
ÅA staged process route: ~ 90 % Mg extraction from serpentinite + fast (~10 min) Mg(OH)2 carbonation ~ 70%
Energy input stand-alone ÅA route ~3 GJ/t, ≈ CO2 capture Application at lime kiln, no CO2 capture: ~ 0.9 GJ/t CO2 power in An alternative route with MgSO4 aqueous carbonation appears
simpler, no heat recovery from carbonation, though Finland & Sweden consider CC(U)S under the Baltic Sea:
Dalders Formation may form a jurisdictional challenge
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Two dr. theses 2012
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 25
2.3.2012 13.12.2012
Coming up (June 2014?) I. Romão
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ANNOUNCEMENT
18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 26
ecos2014.abo.fi