Research on the direct mineralization of flue gas CO2 at ETH Zurich - Mischa Werner at the Alternative CCS Pathways Workshop, Oxford Martin School, 27 June 2014

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Mischa Werner, Subrahmaniam Hariharan, Marco Mazzotti
Institute of Process Engineering
Alternative CCS Pathways Workshop
Oxford, June 26-27 2014
Research on the direct mineralization of flue gas CO2
at ETH Zurich

|| 7/14/2014Mischa Werner - D-MAVT - ETH Zurich - werner@ipe.mavt.ethz.ch 2
mineralizedCO2
natural
minerals
flue gas CO2
high pressure
mineralization
plant
mechanical
activation
capture plant
& compression
pure CO2 mineralizedCO2
natural
minerals
flue gas CO2
high pressure
mineralization
plant
mechanical
activation
capture plant
& compression
pure CO2
additives
recovery
pH-tuning
additives
mineralizedCO2
natural
minerals
flue gas CO2
high pressure
mineralization
plant
mechanical
activation
capture plant
& compression
pure CO2
additives
recovery
pH-tuning
additivesmore reactive minerals
and industrial wastes mechanical
activation
mineralizedCO2
natural
minerals
flue gas CO2
high pressure
mineralization
plant
mechanical
activation
capture plant
& compression
pure CO2
additives
recovery
pH-tuning
activation
thermal
activation
mineralizedCO2
natural
minerals
flue gas CO2
high pressure
mineralization
plant
mechanical
activation
capture plant
& compression
pure CO2capture plant
& compression
additives
recovery
pH-tuning
activation
thermal
activation
high pressure
mineralization
plant
mechanical
activation
thermal
activation
additives
recovery
mechanical
activation
*e.g. McKelvy et al., 2004, Environ Sci Technol 38;
O’Connor et al., 2005, DOE/ARC-TR-04-0024
*
mineralizedCO2
natural
minerals
flue gas CO2
high pressure
mineralization
plant
mechanical
activation
capture plant
& compression
pure CO2capture plant
& compression
additives
recovery
pH-tuning
activation
thermal
activation
high pressure
mineralization
plant
mechanical
activation
thermal
activation
additives
recovery
mechanical
activation
geological storage
mineralizedCO2
natural
minerals
flue gas CO2
mechanical
activation
capture plant
& compression
capture plant
& compression
capture plant
& compression
low pressure
mineralization
plant
additives
recovery
pH-tuning
activation
thermal
activation
mechanical
activation
thermal
activation
additives
recovery
mechanical
activation
No!
mineralizedCO2
natural
minerals
flue gas CO2
mechanical
activation
capture plant
& compression
capture plant
& compression
capture plant
& compression
low pressure
mineralization
plant
additives
recovery
pH-tuning
activation
thermal
activation
thermal
activation
No!
mineralizedCO2
natural
minerals
flue gas CO2
mechanical
activation
capture plant
& compression
capture plant
& compression
capture plant
& compression
low pressure
mineralization
plant
additives
recovery
pH-tuning
activation
thermal
activation
No!
Direct flue gas CO2 mineralization ̶ Motivation
Motivation ─ Activation ─ Dissolution ─ Precipitation ─ Carbonation

||
Fo
Fo
Fo
Fo
Fo
Fo
Fo
Fo FoFo Li Li
Li
LiLi
α-phase Lizardite
Forsterite
Hematite
5 10 15 20 25 30 35 40 45 50 55 60
Intensity[arb.units]
2 Theta [deg]
He
He
7/14/2014Mischa Werner - D-MAVT - ETH Zurich - werner@ipe.mavt.ethz.ch 3
Direct flue gas CO2 mineralization ̶ Activation
Mg3Si2O5 OH 4 Mg3Si2O6.5 OH + 1.5H2O
Mechanical & thermal activation of lizarditeserpentine activated feed
 Capture integration should allow to intensify the pretreatment of precursor material
particle size = -125 µm
heat activation @ T = 610o
C
dehydroxylation = 75%

 Parametric study on activated serpentine dissolution: Liquid and gas flow-through setup
Direct flue gas CO2 mineralization ̶ Dissolution
Werner et al.,
2014, Chem Eng J

 Parametric study on activated serpentine dissolution
lean pCO2lean T
Direct flue gas CO2 mineralization ̶ Dissolution
Multiple layers
in a particle i :
Multiple dissolving
species j :
compact
core
porous shell
( )( )shell core
, , ,
d
=
d
k
r j k i j i j j k
i j
c
V S S r Qc
t
ν + −∑∑
and kinetic modeling
Werner et al., 2014, Chem Eng J
Hariharan et al., 2014, Chem Eng J
Alteration of physical morphology…
… & of chemical compostition:
shell
,i jS
core
,i jS
Material balance for solute k (Mg or Si):
Specific dissolution rates rj :
( )= ,jr f T pH
Surface complexation model
Speciation model
 >80% in 100 min: activated serpentine
dissolves rapidly even at lean T and pCO2

 Ternary phase diagram for the MgO–CO2–H2O system
Direct flue gas CO2 mineralization ̶ Precipitation
and solubility surfaces
Nesquehonite
Hydromagnesite
 Change from precipiation of a more
soluble carbonate at lower T to the
formation of a less soluble but thermo-
dyn. more stable carbonate at higher T

Direct flue gas CO2 mineralization ̶ Carbonation
30o
C 50o
C 60o
C 90o
C
Fast forward
 Parametric study (T, solid/liquid ratio) in single-step batch mode
Werner et al., Phys Chem Chem Phys, submitted

Fast forward
 Parametric study (T, solid/liquid ratio) in single-step batch mode
Insight into precipitation regime in the aS–CO2–H2O system
(1) Mg & Si re-precipiation and (2) equilibrium effects hinder reaction progress
 Investigation of possible improvements:
Concurrent grinding
issue (1)
Carbonate seeding
issue (1)
Sequential feed addition
issue (2)
Double-step carbonation
issue (2)
Carbonation efficiency improved, but each strategy
tackles only one of the two issues at the same time
Play

 A double-step process combining a temperature swing with a pCO2 swing

 Feasibility assessment for the proposed T-pCO2-swing process: illustrative simulations

 Feasibility assessment for the proposed T-pCO2-swing process: through experiments

 Feasibility assessment for the proposed T-pCO2-swing process: double-step experiments
 Pure Mg-carbonate product:

||
Conclusions
Mischa Werner/IPE ETHZ/werner@ipe.mavt.ethz.ch
 Thermal activation effective to promote serpentine reactivity
 High extent of dissolution in less than 100 min
 Our model sheds light on corresp. dissolution mechanism and kinetics
 There is a route to the direct mineralization of flue gas CO2
 Activated serpentine can be carbonated under very lean operating
conditions: ≤ 100o
C and ≤ 1 bar pCO2
 The MgO-CO2-H2O systems allows to exploit a simple T-swing in
combination with a pCO2 swing for successful process design
 Feasibility of this concept proven by simulations and through experiments
 Ultimate performance of the proposed route will be the outcome
of a complex optimization process.

||
 Activation E-requirements
 Precipitation in the aS-CO2-H2O system
 Single-step carbonation
 Concurrent grinding
 Additional illustrative simulations
 Double-step carbonation
Back-ups

||
Fo
Fo
Fo
Fo
Fo
Fo
Fo
Fo FoFo Li Li
Li
LiLi
α-phase Lizardite
Forsterite
Hematite
5 10 15 20 25 30 35 40 45 50 55 60
2 Theta [deg]
He
He
Mechanical & thermal activation of lizarditeserpentine activated feed
C
13 kWh/tonsh
206 kWh/tonsh
120 kWh/tonsh
-75 µm, lizardite serpentine (Gerdemann et al., 2001 Env Sci Tech)
up to 630o
C, cp = 89 cal/mol/K, antigorite (King et al., 1967, RI6962)
100% dehydrox. (Govier and Arnold, 2004, ARC internal rep.)
339 kWh/tonsh $$$/tonsh
Electricity as heat source, no heat integration
(Gerdemann et al., 2001 Env Sci Tech)
Back-ups

||
Fo
Fo
Fo
Fo
Fo
Fo
Fo
Fo FoFo Li Li
Li
LiLi
α-phase Lizardite
Forsterite
Hematite
5 10 15 20 25 30 35 40 45 50 55 60
2 Theta [deg]
He
He
serpentine activated feed
C
13 kWh/tonsh
206 kWh/tonsh
120 kWh/tonsh 570 MJ/t, 80% heat recovered,
20% residual hydroxyls,
Balucan et al., 2013, Int J GHG control339 kWh/tonsh
158 kWh/tonsh 1.2 A$/tonsh
nat. gas as heat source,
accounting for secondary emissions
Mechanical & thermal activation of lizardite
Back-ups

||
Mg-carbonate identification in product: SEM and Raman
 Conditions: S/L = 10% wt., pCO2 = 1 bar, 10 h
Activated serpentine-CO2-H2O system
10001050110011501200
Raman shift [cm-1]
90°C
10001050110011501200
Raman shift [cm-1]
60°C
10001050110011501200
0
4
3
2
1
Raman shift [cm-1]
time[h]
30°C
hydromagnesitenesquehonite
hydromagnesitenesquehonite
5 µm 5 µm 5 µm
90°C60°C30°C
9
8
7
6
5
Back-ups

Parametric study on single-step carbonation
Back-ups

Single-step carbonation
Reproducibility at T = 30°C, S/L = 20% wt., pCO2 = 1 bar
Back-ups

Single-step carbonation with concurrent grinding
 Upgrading a ball mill drum to yield ‘reactor’:
Back-ups

Additional illustrative simulations
Back-ups
 Dissolution of act. serpentine in R1 in flow through mode (f.f.eq. dissolution model used,
no dissolution once solubility of Si-precipitate or Mg-carbonate reached)

Back-ups

CO2 mineralization
Natural process: Industrial application:
1. CO2 dissolution and speciation:
CO2(g) + H2O HCO3
−
+ H+
Mg3Si2O5 OH 4 + 6H+
3Mg2+
+ 2SiO2 + 5H2O
2. Cation extraction from Mg/Ca-rich source:
Mg2+
+ 2HCO3
−
MgCO3 + CO2 + H2O
3. Carbonate precipitation:
serpentine
limestone
activated feed
Carbonate raw
material
CO2 in flue gasCO2 from air
 Enabling utilization (added-value) and permanent storage (CO2 mitigation)
high pCO2, low T
low pH, high T
high pH, high T

CO2 mineralization
CO2(g) + H2O HCO3
−
+ H+
Mg3Si2O5 OH 4 + 6H+
3Mg2+
+ 2SiO2 + 5H2O
Mg2+
+ 2HCO3
−
MgCO3 + CO2 + H2O
serpentine
limestone
activated feed
Carbonate raw
material
high pCO2, low T
low pH, high T
high pH, high T
preliminary
capture step
additives
(recoverable)
feed
activation

CO2 mineralization with capture integration
CO2(g) + H2O HCO3
−
+ H+
Mg3Si2O5 OH 4 + 6H+
3Mg2+
+ 2SiO2 + 5H2O
Mg2+
+ 2HCO3
−
MgCO3 + CO2 + H2O
serpentine
limestone
activated feed
Carbonate raw
material
 Capture integration permits intensification of feed activation or use of pH-tuning additives
low pCO2, low T
low pH, high T
high pH, high T
capture
integration
additives
(recoverable)
feed
activation

Research on the direct mineralization of flue gas CO2 at ETH Zurich - Mischa Werner at the Alternative CCS Pathways Workshop, Oxford Martin School, 27 June 2014

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Research on the direct mineralization of flue gas CO2 at ETH Zurich - Mischa Werner at the Alternative CCS Pathways Workshop, Oxford Martin School, 27 June 2014