Mineralisation of CO using serpentinite rock - towards ... and Steel 2 Secured... · Mineralisation...

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

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


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


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


CCUS / CCS in / for Finland


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

CO2 mineralization: what, how


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

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


Lackner, Science vol. 300, 2003, 1677-1678

CO2 mineralization potential: Oman


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)

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!


Meri-Pori power plant (2.5 Mt CO2/y)

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


Closed loop process producing Mg(OH)2 from Mg-silicate rock


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

Mg(OH)2 carbonation @ ÅA 2007: the fluidised bed set-up


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?

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)


~ 20 bar CO2 → ~ 58 bar CO2

Fagerlund 2009, 2010

scCO2: no

advantage (tests up to

~80 bar)

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 ?!


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

Process energy use


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

Progress towards >90% conversion


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

Conversion of Mg(OH)2 to MgCO3 and MgO in (wet) CO2 or CO2 diluted with (26-72%) N2.


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

Application at a lime kiln ~ 200 kg CO2 / h


Challenge: Diopside

Mg-silicate carbonation at a lime kiln

18/11/2013 Åbo Akademi University |Thermal and Flow Engineering | 20500 Turku 19


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

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




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


Iron (hydroxy) oxide and hydromagnesite can be

precipitated separately or not


N22 l/min

NH3

H2ON2

(SO2)

T = 440 °C

AS + S Mg2+ Fe2+ SO42-

CO2

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


Two dr. theses 2012


2.3.2012 13.12.2012

Coming up (June 2014?) I. Romão

ANNOUNCEMENT


ecos2014.abo.fi

Mineralisation of CO using serpentinite rock - towards ... and Steel 2 Secured... · Mineralisation...

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