Mineralisation of CO2 using serpentinite rock - towards industrial application

Ron Zevenhoven and co-workers; presented by Mikko Helle Åbo Akademi University, ,

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 1 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

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 2 Research areas Cleen Oy CCSP 17 industrial + 9 research partners, 1.1.2011 – 31.12.2015, ~ 5 x 3 M€ 1. CCS concepts 4. Storage solutions

– CHP (Combined Heat and – CO2 storage capacity assesment Power) of the – Other industries – Storage monitoring – Bio-CCS – Mineralisation 2. Capture solutions 5. New ways to utilize – Oxy-fuel combustion CO2 – Looping technologies – Post-combustion capture – Algae cultivation – Emission measurements – Fuel components – Precipitated calcium carbonate 3. Transport of CO2 and intermediate 6. Regulatory complience, storages acceptability of CCS and other common aspects Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 3 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

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 4 CCUS / CCS in / for Finland

In Finland Near Finland / abroad earlier: ”CCS” 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?)

”CCU” CO2 utilisation Several applications Projects ongoing (PCC, CO2 solvent...) US Projects ongoing

* Carbon capture, utilisation and storage, or Carbon capture, use and sequestration

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 5 CO2 mineralization: what, how

Process energy

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

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 6 CO2 mineralization potential Lackner, . Science vol. 300, Much larger potential 2003, 1677-1678 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

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 7 CO2 mineralization potential: Oman

Olivine-containing rock in Oman (350 × 40 x 5 km, ~30% olivine) Pictures:

Kelemen & Matter, PNAS 2008) R Hunwick Presented in Sydney, March 12, 2012

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 8 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, Meri-Pori Lithuania (South-Africa) power plant (2.5 Mt CO2/y) . ”Capture” appears to make CCS too expensive operate on flue gases directly!

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 9 Mg-silicate carbonation: the ÅA route

Mg-extraction Mg(OH)2 production MgCO3 production Magnesium silicate mineral (e.g. serpentinite) Steam

HEAT

NH3 + H2O

Magnesium- AS + Mg-silicate Pressurised MgSO etc. (and iron) Mg(OH)2 fluidised bed MgCO reactor 4 3 extraction > 20 bar, > 500°C

AS Ammoniumsulphate recovery AS CO SiO2 2 + unreacted (pure or flue gas) Iron oxide (→ iron/steel industry)

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 10 Closed loop process producing

Mg(OH)2 from Mg-silicate rock

Oven chamber Specific surface 40 – 50 m2/g Pore volume 20 – 25 cc/g Reactor 3 pH ~8.5 pH ~11.5 pH ~11.5 pH ~8.5

Nduagu, dr. thesis ÅA 2012

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 11 Mg(OH)2 carbonation @ ÅA 2007: the fluidised bed set-up

CO2 P OUT H2O FILTER SAMPLE FEED T CYCLONE

T SAMPLE T COLLECTING FLOW- BED PRE-

METER T FLUIDISED HEATER T

2 m ΔP-GAUGE P Pdif T CO2

H2O

3 m Preheater Research questions: 1) No build-up of MgCO3 on Mg(OH)2 particles?, 2) Fast kinetics? 3) What about supercritical CO2?

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 12 Mg(OH)2 carbonation – results using Dead Sea Periclase material (BET ~ 5 - 8 m2/g)

~ 20 bar CO2 → ~ 58 bar CO2 1.00

unusually high Mg(OH)2 MgO 0.80 MgCO3

Mg(OH)2

- wt) scCO2: 0.60 no advantage (tests up to 0.40 ~80 bar) Composition (% 0.20

0.00 470 480 490 500 510 520 530 540 550 560 Temperature (°C) Fagerlund 2009, 2010

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 13 PFB carbonation of Mg(OH)2

Most tests with Dead Sea Periclase

~ 45 m2/g

x Mg(OH)2 from Portuguese serpentinite T: up to ~ 600°C x (Bragança) June 2013

pCO2: up to 80 bar

. Competition between dehydroxylation and carbonation

– Improve precipiation conditions, control Mg(OH)2 properties – Circulating PFB would allow for finer particles ?! Fagerlund, dr. thesis ÅA 2012

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 14 Process energy use

Reaction Enthalpies Mechanical vapour recompression (MVR) 300 250 crystallization for AS salt recovery 200

H (kJ/mol) 150

Δ MVR compression work ~1.2 GJ/t CO 100 Mg(OH)2 + CO2 2 50 Serpentine + AS 0 Serpentinite rock + AS -50 -100

Reaction enthalpy 0 200 400 600 800 1000 Temperature (°C)

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

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 15 Progress towards >90% conversion 50% 90% 100% 100% 90%

9/2013

Carbonation 3/2012 of extracted Mg

1/2010 50%

Next challenge: 6/2009 >> 90% recovery of ammonium 8/2008 sulphate salt

4/2007 Mg extraction from rock 100%

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 16 Conversion of Mg(OH)2 to MgCO3 and MgO in (wet) CO2 or CO2 diluted with (26-72%) N2.

1.00 1.00 No nitrogen No nitrogen Added nitrogen Added nitrogen 0.80 0.80

0.60 0.60 content content - - 0.40 3 0.40 MgO MgCO 0.20 0.20

0.00 0.00 1.00 0.80 0.60 0.40 0.20 0.00 1.00 0.80 0.60 0.40 0.20 0.00

Mg(OH)2-content Mg(OH)2-content

Total pressure 10 – 59 bar, temperature 450 - 550°C, time 15 minutes

Dead Sea Periclase (DSP) Mg(OH)2, 212-425 µm

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 17 Application at a lime kiln ~ 200 kg CO2 / h

Challenge: Diopside

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 18 Mg-silicate carbonation at a lime kiln

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku 18/11/2013 19 Mg-silicate carbonation at a lime kiln Integration at an industrial lime kiln, water 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

 Kiln flue gas

AS wet Hot water Rock NH3 DH system

MgCO3  Exit gas

water AS Slotte et al. Rest FeOOH water ENERGY 2013

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 20 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

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 21 Alternative route: MgSO4 carbonation in aqueous solution /2

MgSO solution +VNH4OH Extracted (Mg,Fe)SO4 +VNH4OH 4 pH ~ 10 solution from serpentinite pH ~ 8.5 +VCO2 Hydromagnesite pH = 2.05 Iron precipitation pH ~ 6 precipitation 60 min Filter → → 60 min Filter → → → →

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 22 Alternative route: MgSO4 carbonation in aqueous solution /3

NH3 H2O CO2 N2 (SO2) T = 440 °C

N2 2 l/min 2+ 2+ 2- AS + S Mg Fe SO4

Iron (hydroxy) oxide and hydromagnesite can be precipitated separately   or not 

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 23 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 & consider CC(U)S under the Baltic Sea: Dalders Formation may form a jurisdictional challenge

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 24 Two dr. theses 2012

Coming up (June 2014?)

I. Romão

2.3.2012 13.12.2012

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 25 ANNOUNCEMENT

ecos2014.abo.fi

Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku Finland 18/11/2013 26