Sequestration of carbon dioxide: the mineralization option

Transcription

1 ANNUAL WORKSHOP *Current Challenges in Energy Management* University of Coimbra, Portugal, 19 FEB 2014 Sequestration of carbon dioxide: the mineralization option Ron Zevenhoven prof., PhD ChemEng (TU Delft) Åbo Akademi University, Turku, Finland Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/2014 1

2 Overview CO 2 capture (, utilisation) and storage CCUS/CCS CCUS/CCS methods CCUS/CCS in Finland The ÅA route for stepwise serpentinite carbonation Mg(OH) 2 production from magnesium silicate-based rock & Mg(OH) 2 carbonation as a gas/solid reaction Large-scale application; direct operation on flue gas Alternatively: MgSO 4 carbonation in aqueous solution Finland s Cleen CCSP project Conclusions Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/2014 2

3 CCS and CO 2 mineralisation Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/2014 3

4 CCS and CCUS CCS: Carbon dioxide capture and storage CO 2 emissions mitigation Underground storage, geo-sequestration Ocean storage Mineral carbonation, mineral sequestration CCUS: Carbon dioxide capture, utilisation and storage: with U to generate revenue / cover costs Utilisation of CO 2, for example PCC from steelmaking slag, or enhanced oil / gas recovery (EOR /EGR) Note: for EU directive 2009/31/EC CCS = geo-sequestration Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/2014 4

5 Global CO 2 emissions and mitigation CO2now.org H. Geerlings and R. Zevenhoven Annu. Rev. Chem. Biomol. Eng : Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/2014 5

6 CCS / CCUS methods CO2CRC Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/2014 6

7 CCS: CO 2 capture (IPCC, 2005) 19/02/2014 Åbo Akademi University Thermal and Flow Engineering Turku Finland 7

8 CO 2 absorption process Somewhat problematic for gases that contain oxygen Most used solvent solution: 20-30% MEA in water, energy penalty 3-4 GJ/t CO 2 Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/2014 8

9 Geological storage of CO 2 in saline aquifers Sleipner, Norway, ~ 1 Mt CO 2 /yr since /02/2014 Åbo Akademi University Thermal and Flow Engineering Turku Finland 9

10 Storage of CO 2 in depleted gas/oil fields EOR / EGR Enhanced oil recovery (EOR) in the US using natural CO 2 accumulations Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

11 Storage of CO 2 in unminable coal beds (with methane recovery) Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

12 Ocean storage of CO 2 (questionable..) (IPCC, 2005) Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

13 CO 2 mineralization: what, how Process energy IPCC SRCCS 2005 Chapter 7 Overall carbonation chemistry, with M = Mg or Ca (or Fe,...) MO.ySiO 2.zH 2 O (s) + CO 2 (g) < = > MCO 3 (s) + ysio 2 (s) + zh 2 O (l) + HEAT Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

14 CO 2 mineralization potential Much larger potential than other CCUS options, for example: Olivine-containing rock in Oman ( 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, Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

15 CO 2 mineralization potential: Oman Olivine-containing rock in Oman ( x 5 km, ~30% olivine) Kelemen & Matter, PNAS 2008) Pictures: R Hunwick Presented in Sydney, March 12, 2012 Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

16 Commercial Application of CCS end of 2013 Nat. Gas. Coal Gasif. Nat. Gas. Nat. Gas. Nat. Gas. ( ) Incl. 13x EOR/EGR USA/Canada In Europe: (October 2013 = July 2013) 2 projects operational, 13 planned Pix from a presentation by N. Røkke, Oslo, See also GHGT-10 (Amsterdam, Sept. 2010) Summary Report, page 9 Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

17 CCS worldwide: active vs planned Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

18 9 projects operational Current status: carbon capture journal Sept/Oct 2013 Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

19 EOR Mtpa Saline Aquifers 2.7 Mtpa 9 projects operational Current status: carbon capture journal Sept/Oct 2013 EOR EOR EOR EOR EOR EOR Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

20 CCUS / CCS in / for Finland earlier: CCS CCU * Carbon capture, utilisation and storage, or Carbon capture, use and sequestration Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

21 CO 2 mineralisation: the ÅA route Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

22 CO 2 mineralisation in Finland For Finland the only CCS option in or close to the country is CO 2 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 CO 2 /y) Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

23 Mineral resources; source-sink links Vammala Mg-silicate resources (~200 Mt rock) ~85 km Meri-Pori power plant (2.5 Mt CO 2 /y) Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

24 Mg-silicate carbonation: the ÅA route AS = ammonium sulphate Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

25 Closed loop process producing Mg(OH) 2 from Mg-silicate rock Oven chamber Reactor 3 ph ~8.5 ph ~11.5 Specific surface m 2 /g Pore volume cc/g Nduagu, dr. thesis ÅA 2012 Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

26 Mg(OH) 2 ÅA 2007 : the fluidised bed set-up 2 m FLUIDISED BED Research questions: 1) No build-up of MgCO 3 on Mg(OH) 2 particles?, 2) Fast kinetics? 3) What about supercritical CO 2? Preheater Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

27 Mg(OH) 2 carbonation results using Dead Sea Periclase material (BET ~ 5-8 m 2 /g) ~ 20 bar CO 2 ~ 58 bar CO 2 scco 2 : no advantage (tests up to ~80 bar) Fagerlund 2009, 2010 Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

28 PFB carbonation of Mg(OH) 2 Most tests with Dead Sea Periclase ~ 45 m 2 /g T: up to ~ 600 C p CO2 : up to 80 bar x x Mg(OH) 2 from Portuguese serpentinite (Bragança) June 2013 start goal 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 Turku Finland 19/02/

29 Process energy use 300 l) o 250 /m J 200 (k H 150? y 100 a lp 50 th e n 0 n e a c tio R Reaction Enthalpies Mg(OH)2 + CO2 Serpentine + AS Serpentinite rock + AS Temperature (\C) Mechanical vapour recompression (MVR) crystallization for AS salt recovery MVR compression work ~1.2 GJ/t CO 2 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 ~3 GJ (mainly 400 C heat) and ~3 t rock per ton (1000 kg) CO 2 Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

30 Progress towards >90% conversion 50% 90% 100% 100% 90% Carbonation of extracted Mg 3/2012 9/2013 1/ % Status 14 Oct /2008 6/2009 Next challenge: >> 90% recovery of ammonium sulphate salt 4/2007 Mg extraction from rock 100% Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

31 Conversion of Mg(OH) 2 to MgCO 3 and MgO in (wet) pure CO 2 or CO 2 diluted with (26-72%) N 2. Total pressure bar, temperature C, time 15 minutes Dead Sea Periclase (DSP) Mg(OH) 2, µm Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

32 Application at a lime kiln ~ 200 kg CO 2 / h Challenge: Diopside Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

33 Mg-silicate carbonation at a lime kiln Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

34 Mg-silicate carbonation at a lime kiln water Integration at an industrial lime kiln, no CO 2 capture, full flue gas compression to 80 bar ~ 20 bar CO 2, 0.2~0.25 t CO 2 /h fixed, heat (kiln gas) 2.6 GJ/t, power 0.9 GJ/t CO 2 Kiln flue gas AS Rock wet NH 3 Hot water DH system MgCO 3 Exit gas water Rest FeOOH water AS Slotte et al. ENERGY 2013 Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

35 CO 2 mineralisation: cooperation Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

36 The Baltics: Lithuania, Estonia The Varena region in Lithuania contains good quality serpentinites (Stasiulatiene, GHGT-9) Large amounts (10-15 Mt/y) of calcium-based oil shale ashes can be carbonated. Besides CaO currently also Ca, Mg silicates are studied (Kuusik, Uibu, Velts) ~280 Mt ash in ash ponds Åbo Akademi University - Thermal and Flow Engineering Laboratory Piispankatu 8, Turku FINLAND /64

37 Portugal s interest in CO 2 mineralisation CO 2 emissions ~ 65 Mt/a Large mineralisation resources; Bragança area resources can fix a lot of CO 2 Seismic activity in the south of the country... Romaõ et al., CleanAir 2011 Åbo Akademi University - Thermal and Flow Engineering Laboratory Piispankatu 8, Turku FINLAND

38 Singapore s interest in CO 2 mineralisation National Geographic Åbo Akademi University - Thermal and Flow Engineering Laboratory Piispankatu 8, Turku FINLAND

39 CO 2 mineralisation: the alternative ÅA route Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

40 Alternative route: MgSO 4 carbonation in aqueous solution /1 +: No need to produce and carbonate Mg(OH) 2 +: No CO 2 capture stage, no NH 3 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 Turku Finland 19/02/

41 Alternative route: MgSO 4 carbonation in aqueous solution /2 Extracted (Mg,Fe)SO 4 solution from serpentinite ph = 2.05 MgSO 4 solution +V CO2 ph ~ 6 Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

42 Alternative route: MgSO 4 carbonation in aqueous solution /3 T = 440 C NH3 H2O N2 (SO2) CO2 N2 2 l/min AS + S Mg 2+ Fe 2+ SO4 2- Iron (hydroxy) oxide and hydromagnesite can be precipitated separately or not Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

43 Other CCS activities in Finland Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

44 Research areas Cleen Oy CCSP 17 industrial + 9 research partners, , ~ 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 CO 2 and intermediate storages 3. Storage solutions CO 2 storage capacity assesment of the Baltic Sea Storage monitoring Mineralisation 4. New ways to utilize CO 2 Algae cultivation (~ India cooperation) Fuel components Precipitated calcium carbonate 5. Regulatory complience, acceptability of CCS and other common aspects Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

45 CO 2 storage capacity assessment of the Baltic Sea Research collaboration with the Swedish CCS project (Bastor2) A first estimate on the geological storage potential of CO 2 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: Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

46 Conclusions CO 2 mineral sequestration offers a leakage-free alternative for CO 2 underground storage worldwide; only option in Finland CO 2 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: ~ 80 % Mg extraction from serpentinite + fast (~10 min) Mg(OH) 2 carbonation ~ 70% Energy input stand-alone ÅA route ~3 GJ/t, CO 2 capture Application at lime kiln, no CO 2 capture: ~ 0.9 GJ/t CO 2 power in An alternative route with MgSO 4 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 Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

47 Two dr. theses 2012 Coming up (Spring 2014?) I. Romão Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/

48 Acknowledgements & support from Åbo Akademi University Thermal and Flow Engineering Turku Finland 19/02/