Mineralization:

CO2 Conversion to Carbonates for

CO2 Utilization and Storage
Greeshma Gadikota
Dept. of Chemical Engineering & Dept. of Earth and Environmental Engineering
Lenfest Center for Sustainable Energy
Columbia University in the City of New York
New York, NY
RECS
June 10, 2015

CO2 Capture Materials

Novel Materials

(NETL, 2011)

Song at Penn State

q MEA Challenges

Corrosion and solvent degradation

High capital and operating costs

High parasitic energy penalty

Giannelis at Cornell and Park at Columbia

2

Solid Sorbents & Chemical Looping Technologies

Carbonation / Calcination cycle

Oxidation / Reduction cycle

Water-Gas Shi-:
CO + H2O !" H2 + CO2

Micro- vs. Mesopores

MO + CO2 MCO3

MO + CO M + CO2

MCO3 MO + CO2

M + H2O MO + H2

KIERs 100kW CLC

system (2006-2011)

e.g., ZECA process

e.g., Chemical Looping process for H2 production

(Los Alamos National Lab)

(Ohio State Univ.: U.S. Patent No. 11/010,648 (2004))

CO2 Utilization
Challenges and Opportunities

Carbonate formation is thermodynamically

favored

Using CO2 as an alternative processing

fluid for unconventional hydrocarbon
extraction reduces the need for water

(NETL, 2011)

Carbon Storage Schemes

Gas Processing PlaBorms

U8liza8on

Capture

1 million tons of CO2

injected every year since
2006

Storage

q Ocean storage

CO2 Injec8on Well

q Biological fixation
q Geologic storage

Statoils Sleipner West

Gas reservoir in the
North Sea

USD 100,000 saved

daily on CO2 tax
Graphic courtesy of Statoil
(Geo3mes, 2003)

q Mineral carbonation

In Salah Gas Project in Algeria

600,000 tons of CO2
injected every year since
2004

Mimics natural chemical transformation of CO2

MgO + CO2 MgCO3

Graphic courtesy of BP
(Geo3mes, 2003)

Thermodynamically stable product & Exothermic reaction

Appropriate for long-term environmentally benign and unmonitored storage

Research Objectives
Develop transformative approaches towards sustainable
energy with integrated carbon capture, utilization, and storage

Comprehensive understanding of CO2 interactions with natural and

engineered materials
Closing the carbon cycle within energy conversion processes via
engineered carbonation using both its own wastes and natural sources
Enable efficient extraction of unconventional energy sources (e.g.,
shale) with combined CO2 storage
Understanding of long-term fate of injected CO2 in the earth system
6

Various Materials for Carbon Fixation

Availability
silicate minerals >> industrial wastes

Crystallinity
industrial wastes < minerals
Reactivity
industrial wastes > minerals
Pre-processing requirements
(e.g., mining, crushing etc.,)
industrial wastes < minerals

Source: Kurt Houz

Carbonation of industrial wastes results in reclassification of these materials as non-hazardous

hence safe for landfilling and for long-term carbon storage

Carbon Mineralization

CO2 Conversion to Carbonates

Source: Gadikota and Park, 2014, Carbon Dioxide Utilization, 1st Edition, Elsevier

Source: Gadikota et al., 2014, Journal of Hazardous Materials

q Develop technologies to integrate carbonation of industrial wastes at the site of CO2 generation
q Determine the fate of hazardous components such as Cr, Ni during carbonation
q Use CO2 to treat hazardous Asbestos Containing Materials (ACM)
9

Worldwide Availability of
Ca and Mg-bearing Alkaline Materials for CCUS

Belvidere Mountain, Vermont

Serpentine Tailings

Mineral Carbonation of
Peridotite

Photo by Dr. Jrg Matter at

LDEO (2008)

10

Effect of Chemical Composition on CCS Storage Potential

100

In-Situ CO2
Storage

Shorter time scales

(~hours)

Longer time scales

(~years)

Limited spatial scale

Larger spatial scale

with utilization of
earth as a reactor
(~hundreds of miles)

Relatively
homogenous
mineralogy

Heterogeneous
mineralogy

40

More flexible tuning

in reaction
conditions

Not limited by
reactor size; Use of
geothermal gradient

20

Possible production
of value-added
products

Multiple CO2
trapping
mechanisms

No monitoring
required

Relatively
economical at this
time

80
E x te n t of C a rb on a tion (% )

Ex-situ CO2
Storage

Experiments performed at 185oC, PCO2 of 150 atm in

1.0M NaCl+0.64M NaHCO3. 15 wt. % solid
Reaction time:
0.5 hr

1 hr

4 hr

4 hr dry attrition grinding

All others 1 hour dry attrition grinding
60

OConnor et al., AAPG Annual Meeting, 2003

0
Magnetite A northite

B as alt

T alc

A ugite

L izardite

Alumino-silicates
Abundance of less reactive
minerals vs. limited availability
of highly reactive minerals

A ntigorite

F ayalite

F ors terite W ollas tonite

Silicates
Carbonation efficiency defines
whether mineral is utilized for
ex-situ or in-situ storage

11

Direct vs. Two-Step Carbonation

Gadikota and Park, 2014, Carbon Dioxide Utilization, 1st Edition, Elsevier

12

Synthesis of High Purity Products and By-Products

Mg-bearing Silicates

Ca-bearing Silicates

(Mg,Fe)2SiO4 and (Mg,Fe)3(OH)4(Si3O5)

Mg-Carbonate
Phases

Geothite
(a-FeO(OH))

(CaSiO3)

Silica
(SiO2)

Ca-Carbonate
Phases

Nesquehonite
(MgCO3.3H2O)

Vaterite

30 m

Hydromagnesite
(Mg5(CO3)4(OH)24H2O)

1 m

500 nm

Products of the pH swing process where silica is

obtained at pH ~2, geothite is precipitated at pH
~8.6, and magnesium or calcium carbonate at pH ~
10.

1 m

Aragonite

30 m

1 m

Increasing temperature and PCO2 favor the

formation of anhydrous magnesium carbonate
phases such as magnesite (MgCO3).

Magnesite
(MgCO3)
30 m

Calcite

Optimal conditions for forming calcite are pH > 12,

aragonite at pH 11, and vaterite at a pH between
9.0 and 9.5.

1 m

Gadikota et al., 2014, Green Building Materials (Book Chapter) Submitted

Achieving high degree of control over

desired chemical and morphological composition
for CO2 utilization remains a challenge
Gadikota and Park, 2014, Carbon Dioxide Utilization, Elsevier

13

Fundamental Challenges in Carbon Mineralization

Inadequate and inaccurate kinetic data
Variability in rates fast, initial kinetics vs. long-term, slow kinetics
Formation of mass transfer limiting passivation layers
Competing reactions challenging to produce pure components
Formation of meta-stable carbonates
Considerable heterogeneity in the starting materials and product phases
pH control with additives needed
Modeling and prediction uncertainties

Need for novel reactor systems and

comprehensive material characterization
14

Fundamental Challenges in Carbon Mineralization

Inadequate and inaccurate kinetic data
Variability in rates fast, initial kinetics vs. long-term, slow kinetics
Formation of mass transfer limiting passivation layers
Competing reactions challenging to produce pure components
Formation of meta-stable carbonates
Considerable heterogeneity in the starting materials and product phases
pH control with additives needed
Modeling and prediction uncertainties

Need for novel reactor systems and

comprehensive material characterization
15

Better Design of Kinetic Studies for Complex Reactions

Gadikota et al., I&ECR 2014

16

Dissolution Kinetics & Rate Laws for Magnesium Silicate

Ea = 52.9 kJ/mol

Ea = 31 kJ/mol

Our rate law:

rMg ,dis1 (mol / cm .s) = 10

( 0.1

2042
)
T (K )

+ 0.5

(H )

+ 0.003 10

2
+ 0.46
Hanchens rate law: r
e
Mg ,dis 2 (mol / cm .s ) = 0.0854 ( H )

Magnesite
Precipitation Rate:
(Saldi et al., 2012)

rMg , precip (mol / cm 2 .s) = kMg

(

( 2.5

6362.76
T (K )

KCO3 KOH
KOH aCO 2 + KCO3 KOH + KCO3 aOH
3

2042
)
T (K )

) M (1 MMg )
17

Fundamental Challenges in Carbon Mineralization

Inadequate and inaccurate kinetic data
Variability in rates fast, initial kinetics vs. long-term, slow kinetics
Formation of mass transfer limiting passivation layers
Competing reactions challenging to produce pure components
Formation of meta-stable carbonates
Considerable heterogeneity in the starting materials and product phases
pH control with additives needed
Modeling and prediction uncertainties

Need for novel reactor systems and

comprehensive material characterization
18

Metastability in MgO-CO2-H2O System

Magnesite is the most stable and

least soluble carbonate under most

conditions (including PCO2)

Despite this, magnesite is seldom

the main product reported in
literature:

-
-
-
-
-

Brucite: Mg(OH)2
Lansfordite: MgCO35H2O
Nesquehonite: MgCO33H2O
Hydromagnesite: Mg5(CO3)4(OH)24H2O
Magnesite: MgCO3

Driven by reaction kinetics, given

enough time, magnesite should
form

Swanson et al., PCCP 2014

19

Significant Complexity in Mg-CO2-H2O Systems

Maximum saturation index () achievable under the

experimental conditions reported in 23+ publications

Significant variety in carbonate formation over similar

reaction conditions

Swanson et al., PCCP 2014

" IAP %
= log $
'
# K SP &
!

20

Effect of Temperature on Mg(OH)2 Slurry Carbonation

Biggest factor influencing phase

is Temperature
Easily distinguishable by TGA
and XRD analyses
Fricker et al., I&ECR 2014

Magnesite:
MgCO3
Hydromagnesite: Mg5(CO3)4(OH)24H2O
Nesquehonite:
MgCO33H2O
21

Effect of Temperature on Mg(OH)2 Slurry Carbonation

At 30 C
Make Nesquehonite

Fricker et al., I&ECR 2014

At 150 C
Make Hydromagnesite

At 200 C
Make Magnesite

22

Effect of Seeds on Mg(OH)2 Slurry Carbonation

Carbonation at
150 C for 120 min

Mg(OH)2

Al2O3

MgCO3

Starting materials
Swanson et al., PCCP 2014

23

Fundamental Challenges in Carbon Mineralization

Inadequate and inaccurate kinetic data
Variability in rates fast, initial kinetics vs. long-term, slow kinetics
Formation of mass transfer limiting passivation layers
Competing reactions challenging to produce pure components
Formation of meta-stable carbonates
Considerable heterogeneity in the starting materials and product
phases
pH control with additives needed
Modeling and prediction uncertainties

Need for novel reactor systems and

comprehensive material characterization
24

Better Design of Kinetic Studies for Complex Systems

Gadikota et al., I&ECR 2014

25

V olum e (% ) C um ula tive P ore V olum e (m l/g )

10

-2

Effect of Temperature on Magnesium Silicate Carbonation

80
60
40
20

10

-2

10

-3

80

100

120
140
160
o
T e m p e ra ture ( C )

180

200

1 2 5 C
o

1 5 0 C
o

1 8 5 C

9 0 C
o

1 2 5 C

8 -4
10

1 5 0 C
o

1 8 5 C

6 1

10
P ore D ia m e te r (nm )

100

0
1

10

100

1000

Experimental Conditions: PCO2 = 139 atm, 3 hrs,

1.0 M NaCl + 0.64 M NaHCO3, 15 wt% solid, 800 rpm

9 0 C

10

U nre a c te d O liv ine

P a rtic le D ia m e te r ( m )

U nre a c te d O liv ine

-4

10

T G A
T C A
A R C [1 h r]

C um ula tive P ore V olum e (m l/g )

-3

E x te n t of C a rbona tion (% )

100

10

10
P ore D ia m e te r (nm )

Coupled effects of (i) CO2 hydration (ii) mineral

dissolution, and (iii) formation of carbonates are
evident. Increasing temperature aids mineral
dissolution kinetics and reduces the solubility of
magnesite

100

Gadikota et al., PCCP (2014)

26

Formation of anhydrous MgCO3 at lower temperature

(a)
(a)
(a)

Olivine

(b)
(b)

Magnesite

(II)
(II)

R e la tiv e In ten s ity

R e la tiv e In ten s ity

185 C
o

y
ti
s
n
e
t
n
I
e
v
it
a
l
e
R

150 C

CC

(I)(I)
o

125 C

10 m

(b)
(b)

90 C

Gadikota et al., PCCP (2014)

40

50

60

70

80

R e la tiv e In ten s ity

R e la tiv e In ten s ity

30

Mg
Mg

(II)
(II)

U nre a cte d
20

OO

(a)
(a)

0 .10 .1

CC

Magnesite
Magnesite

(I)(I)

SiSi

OO

Mg
Mg

Si-rich
Si-rich
Phase
Phase

10 m

Dominant formation of magnesite (MgCO3)

0 .10 .1

1 1

1 01 0

keke
VV

Hydrous phases such as nesquehonite (MgCO3.3H2O) and hydromagnesite

(Mg5(CO3)4(OH)24H2O) were not formed in the range of 90-185 oC

27

(a)
80
80
60
60
40
40
T G
GA
A
T
T CC A
A
T
A SS U [1 h
U [1 hr]
A
r]

0.5
0.5

1.0
1 .0

1.5
1.5

2.0
2 .0

2.5
2.5

10

- 3

10

- 4

10

- 5

10

- 6

(b)

Mg -e qu ilibrium
C arb ona te - equ ilib rium

0 .0

0 .5

[N
[NaaHHCC O
O 3 ] (M)
] ( M)

(c)

4
4

2
2

0
0

1
1

10

100

1000

P a rtic10
le D ia m e10
te0r ( m ) 1 0 00
P a rtic le D ia m e ter ( m )

Experimental Conditions: 185

oC,

10

2.0

10

Buffering the pH in the range

of 6-7 facilitates dissolution
and carbonation

(d)

- 2

-3

10

10

10

-2

U nre a c te d
D .I.W a te r
Un re ac te d
0.32 M
D .I .W a ter
0.48 M
0. 32 M
0.64 M
0. 48 M
1.00 M
0. 64 M
2.00 M
1. 00 M
2. 00 M

V o lum e ( % )

V olum e (% )

10

1 .5

P ore
V m
olum
(m
C uCmum
u laula
tiv etiv
Peore
V olu
e ( mel/g
) l/g )

10

1.0

[N a H C O 3 ] ( M)

Speciation calculations show

that NaHCO3 buffers pH
(6.4-7.0) and serves as a
carbon carrier

- 3

-4

10

- 4

10

10

P ore D ia m eter (nm )

U nrea c ted
D
.I.Wac
a ter
Unre
ted
0.32 M
D .I .W a ter
0.48 M
0.3 2 M
0.64 M
0.4 8 M
1.00 M
0.6 4 M
1.0 0 M
2.00 M
2.0 0 M

100

100

00
0.0
0 .0

10

- 2

20
20

10

- 1

100
1 00
C on c e ntra tio n (m ol /k g )

E x ten t of C a rb o na tio n ( % )

E x te nt of C a rbona tion (% )

Effect of NaHCO3 on Magnesium Silicate Carbonation

Gadikota et al., PCCP (2014)

P ore D i a m e te r ( n m )

PCO2 = 139 atm, 3 hours, 15 wt% solid, 800 rpm

28

Can we predict the long-term fate of CO2

based on our laboratory data?

Need dissolution and carbonation rate data in addition to

choice of reaction conditions
29

Selected Magnesium Silicate-CO2-Fluid System

(a)(a)

(b) (b)

O
Mg Mg

(2) (2)

10 m

Magnesite
Magnesite
O

Si

Si

Mg Mg

Si-rich
Phase
Si-rich
Phase
0.1 0.1
0.1

11

10
10

10

k eV k eV
keV

(b)

Temperature conditions chosen based on the single step

carbonation rate data (Gadikota, PCCP 2014)
Assume changing volume of rock due to
surface passivation: n <0,
increasing surfaces available (e.g., through fractures): n> 0
no changes: n = 0

Ratetime Vtime
=

Ratetime=0 Vtime=0

Simulations set up in PhreeqC (geochemistry software)

Gadikota et al., to be submitted (2014)

30

(1) (1)

125 oC 150 oC
(Medium) (High)

R ela tiv e In ten s ity

90 oC
(Low)

R ela tiv e In
ten s ity
Relative
Intensity

(a)

Sensitivity Analyses (temperature, degree of fracture

formations, rate constant)
(a)

(b)

Our work
T (oC)

rMg,dis1, t = 0
(mol/m2.s)

90

2.1 x 10-12

125

6.5 x 10-12

150

1.3 x 10-11

Gadikota et al., to be submitted (2014)

(c)

(d)

Hanchen et al.,
T (oC)

rMg,dis2, t = 0
(mol/m2.s)

90

1.4 x 10-11

125

6.7 x 10-11

150

1.7 x 10-10

Hanchen et al., Geochim.

Cosmochim. Ac. (2006)

31

Coupling Kinetic and Transport Phenomena

in Complex Systems
Salinity of fluid
+

pH of fluid

+
pH<5

+
pH>7

Pressure

Temperature
+

Mineral reactivity
+

+ +

+
+
Mineral dissolution

Mineral carbonation

Reactive
surface area

+
+

Porosity
+

Permeability
+
Formation of microfractures

32

Research Objectives
Develop transformative approaches towards sustainable
energy with integrated carbon capture, utilization, and storage

Comprehensive understanding of CO2 interactions with natural and

engineered materials
Closing the carbon cycle within energy conversion processes via
engineered carbonation using both its own wastes and natural sources
Enable efficient extraction of unconventional energy sources
(e.g., shale) with combined CO2 storage
Understanding of long-term fate of injected CO2 in the earth system
33

Global shale gas reserves

Deeper formations
Lack of water

34

Unconventional Energy Sources (e.g., shale)

Technological advancements
q Horizontal drilling
q Hydraulic fracturing

But significant water consumption

and contamination
Possible solutions
q Chemically functionalized
proppants to immobilize heavy
metals
q waterless fracking with gases
such as CO2

Potential carbon storage

But what are the coupled

reactive-transport phenomena
that would impact CO2-shale
interactions?
35

Proposed Interaction of CO2 and Clays (for shale)

q Initial arrangement

of clay matrix
q Before CO2 injection

q CO2 occupies space

created from clay
matrix disruption

q Gas drag force breaks

inter-clay particle
physical bonds
q Clay particles pulled
through pore spaces

q CO2 diffuses into

clay-layered structures
q Changes in interlayer
electrical forces =>
inter-clay break-up

Berrezueta et al., 2013, International Journal of Greenhouse Gas Control

36

Characterization of Various Types of Shales

Components
SiO2
Al2O3
Fe2O3
MgO
CaO
Na2O
K2O
TiO2
P2O5
MnO
Cr2O3
V2O5
LOI
Total Carbon (%)
Organic Carbon (%)
Inorganic Carbon (%)

Non-calcite
Carbonaceous
(wt%)
58.6
21.4
5.1
1.6
0.2
0.3
4.1
1.1
0.1
0.03
0.05
0.03
7.2
1.26
0.74
0.52

Shale
Calcite-bearing
Argillaceous
(wt%)
55.7
17.5
6.6
2.3
3.6
0.2
4.2
0.8
0.1
0.04
0.04
0.04
8.0
1.62
0.67
0.95

Oil-rich
Bituminous
(wt%)
40.3
9.5
4.1
1.7
19.4
0.8
2.1
0.5
0.2
0.05
0.03
0.02
19.4
6.49
2.48
4.01
37

Supercritical CO2 Interaction with Shale

Loring et al., Langmuir, 2012

CO2 intercalation with clays => expansion

CO2 is rotationally constrained and does not appear to react with trapped water

Research Questions
What is the effect of dry vs. wet scCO2?
What are the effects of variable chemical compositions of shale?
Can CO2 be used as an alternative for acid-induced fracking?

38

Effect of CO2 and Water on Pore Volume Changes

Experimental conditions: PCO2 = 150 atm, 80 oC, 3 hr

Combination of water and CO2

=> significant morphological changes

Are these changes

chemically induced ?
39

Effect of CO2 and Water on Chemical Changes

Insufficient acidity to induce significant

chemical changes in Al and oil-rich shales
Phase changes evident in C & Al-rich shales

40

Effect of CO2 and Water on Clay

CO2 interactions with montmorillonite

Espinoza et al., 2012, International Journal of Greenhouse Gas Control

41

Effect of Temperature on Pore Volume Changes

Higher temperatures result in greater

pore volume changes
Utilize the geothermal gradient for
greater energy extraction but deeper
drilling is more expensive
42

Effect of Temperature on Chemical Changes

Some changes in carbonaceous shales

No significant changes in argillaceous
and bituminous shales

How can we accelerate

increase in pore spaces?
43

Acid fracking
Typical shale deposit

Monterey Shale, California

Uneven geological formations

make horizontal drilling harder
Injecting strong acids (e.g.,
HCl) rapidly disorders or
dissolves clays, carbonates etc.,
Environmentally hazardous

Courtesy: The Chronicle

Are there are any alternative benign chemicals that can be used
to induce chemical changes?
44

Effect of Na-citrate and CO2

0.1 M Na-citrate,
pH = 3.0
Unreacted

Reacted

0.1 M Na-citrate,
PCO2 = 150 atm
Unreacted

Calcite-rich

Calcite-rich

Non-calcite

Non-calcite

Oil-rich

Oil-rich

Experiments performed at 80 oC for 3 hours

Reacted

45

Research Objectives
Develop transformative approaches towards sustainable
energy with integrated carbon capture, utilization, and storage

Comprehensive understanding of CO2 interactions with natural and

engineered materials
Closing the carbon cycle within energy conversion processes via
engineered carbonation using both its own wastes and natural sources
Enable efficient extraction of unconventional energy sources (e.g.,
shale) with combined CO2 storage
Understanding of long-term fate of injected CO2 in the earth system
46

Summary
Combination of multi-scale experimental and modeling studies
are needed to develop CCUS technologies
Investigation of coupled physical and chemical phenomena is
essential for predicting the fate of CO2 above and below the
ground
Accurate kinetic and mechanistic data are needed to predict
multi-scale and multi-temporal interactions of CO2 with different
materials
Identification of all processes that emit CO2 and determination of
methods to limit these emissions are needed to close the carbon
balance
47

Acknowledgements
Advisors and Collaborators
Prof. Alissa Park (Columbia)
Prof. Peter Kelemen (Columbia)
Prof. Juerg Matter (Southampton)
Dr. Pat Brady (Sandia)
Prof. Venkat Venkatasubramanian (Columbia)
Dr. Babji Srinivasan (IIT)
Dr. Claudio Natali (IGR, Italy)
Dr. Chiara Boschi (IGR, Italy)

Park Group Members

48